WO2016104214A1

WO2016104214A1 - Compound, resin, underlayer film forming material for lithography, underlayer film for lithography, pattern forming method and purification method

Info

Publication number: WO2016104214A1
Application number: PCT/JP2015/084907
Authority: WO
Inventors: 匠樋田; 越後　雅敏; 佐藤　隆; 牧野嶋　高史
Original assignee: 三菱瓦斯化学株式会社
Priority date: 2014-12-25
Filing date: 2015-12-14
Publication date: 2016-06-30
Also published as: JP7026439B2; EP3239141A1; SG11201705038XA; US10745372B2; IL253109A0; CN107108549A; JPWO2016104214A1; EP3239141A4; TW201629031A; US20170349564A1; KR20170099908A

Abstract

A compound which is represented by formula (1). (In formula (1), each X independently represents an oxygen atom or a sulfur atom, or alternatively represents being non-crosslinked; R¹ represents a single bond or a 2n-valent group having 1-30 carbon atoms, said group optionally having an alicyclic hydrocarbon group, a double bond, a heteroatom or an aryl group having 6-30 carbon atoms; each R² independently represents a linear, branched or cyclic alkyl group having 1-10 carbon atoms, an aryl group having 6-10 carbon atoms, an alkenyl group having 2-10 carbon atoms, an alkoxy group having 1-30 carbon atoms, an aryloxy group having 6-30 carbon atoms, or a hydroxyl group, provided that at least one R² is an alkoxy group having 1-30 carbon atoms or an aryloxy group having 6-30 carbon atoms; each m independently represents an integer of 1-6; each p independently represents 0 or 1; and n represents an integer of 1-4.)

Description

Compound, resin, lower layer film forming material for lithography, lower layer film for lithography, pattern forming method and purification method

The present invention relates to a compound, a resin, an underlayer film forming material for lithography, an underlayer film for lithography, a pattern forming method, and a purification method.

In the manufacture of semiconductor devices, microfabrication by lithography using a photoresist material is performed. In recent years, further miniaturization by pattern rules has been demanded as LSI is highly integrated and increased in speed. Lithography using light exposure, which is currently used as a general-purpose technology, is approaching the essential resolution limit derived from the wavelength of the light source.

The light source for lithography used for resist pattern formation is shortened from KrF excimer laser (248 nm) to ArF excimer laser (193 nm). However, as the miniaturization of the resist pattern progresses, there arises a problem of resolution or a problem that the resist pattern collapses after development. Therefore, it is desired to reduce the thickness of the resist. In response to such a demand, simply thinning the resist makes it difficult to obtain a resist pattern film thickness sufficient for substrate processing. Therefore, not only the resist pattern but also a process of creating a resist underlayer film between the resist and the semiconductor substrate to be processed and providing the resist underlayer film with a function as a mask during substrate processing is required.

Currently, various types of resist underlayer films for such processes are known. For example, unlike a resist underlayer film having a high etching rate, a resist underlayer film for lithography having a dry etching rate selection ratio close to that of a resist can be used. As a material for forming such a resist underlayer film for lithography, it contains a resin component having at least a substituent that generates a sulfonic acid residue when a predetermined energy is applied and a solvent, and a solvent. An underlayer film forming material for a multilayer resist process has been proposed (see, for example, Patent Document 1). Further, a resist underlayer film for lithography having a low dry etching rate selection ratio compared to the resist can be given. As a material for forming such a resist underlayer film for lithography, a resist underlayer film material containing a polymer having a specific repeating unit has been proposed (for example, see Patent Document 2). Furthermore, a resist underlayer film for lithography having a lower dry etching rate selectivity than the semiconductor substrate can be mentioned. As a material for forming such a resist underlayer film for lithography, there is a resist underlayer film material containing a polymer obtained by copolymerizing a repeating unit of acenaphthylenes and a repeating unit having a substituted or unsubstituted hydroxy group. It has been proposed (for example, see Patent Document 3).

On the other hand, as a material having high etching resistance in this type of resist underlayer film, an amorphous carbon underlayer film formed by CVD using methane gas, ethane gas, acetylene gas or the like as a raw material is well known. However, from the viewpoint of the process, a resist underlayer film material capable of forming a resist underlayer film by a wet process such as spin coating or screen printing is required.

In addition, the inventors of the present invention provide a lithographic lower layer containing a naphthalene formaldehyde polymer containing a specific structural unit and an organic solvent as a material that is excellent in optical characteristics and etching resistance and is soluble in a solvent and applicable to a wet process. A film-forming composition has been proposed (see, for example, Patent Documents 4 and 5).

In addition, regarding the formation method of the intermediate layer used in the formation of the resist underlayer film in the three-layer process, for example, a silicon nitride film formation method (for example, refer to Patent Document 6) or a silicon nitride film CVD formation method (for example, Patent Document 7) is known. As an intermediate layer material for a three-layer process, a material containing a silsesquioxane-based silicon compound is known (for example, see Patent Documents 8 and 9).

JP 2004-177668 A JP 2004-271838 A JP 2005-250434 A International Publication No. 2009/072465 International Publication No. 2011/034062 JP 2002-334869 A International Publication No. 2004/066377 JP 2007-226170 A JP 2007-226204 A

As described above, a number of materials for forming a lower layer film for lithography have been proposed, but not only have solvent solubility to which a wet process such as spin coating or screen printing can be applied, but also have heat resistance and etching resistance. There is a need for further improvements in solubility in safe solvents to achieve a high level of compatibility and to stabilize product quality at a high level.

The present invention has been made in view of the above-mentioned problems, and its purpose is useful for forming a photoresist underlayer film, a wet process is applicable, and excellent heat resistance and etching resistance. Another object of the present invention is to provide a compound and resin, a lower layer film forming material, and a pattern forming method, which are further improved in solubility in a safe solvent.

As a result of intensive studies in order to solve the above problems, the present inventors have found that the above problems can be solved by using a compound or resin having a specific structure, and have completed the present invention.

That is, the present invention provides the following [1] to [19].
[1]
The compound represented by following formula (1).

(In the formula (1), each X independently represents an oxygen atom or a sulfur atom, or non-bridged, and R ¹ is a single bond or a 2n-valent group having 1 to 30 carbon atoms, Each may have an alicyclic hydrocarbon group, a double bond, a hetero atom, or an aryl group having 6 to 30 carbon atoms, and each R ² is independently a straight chain having 1 to 10 carbon atoms, A branched or cyclic alkyl group, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, or a hydroxyl group, And at least one of R ² is an alkoxy group having 1 to 30 carbon atoms or an aryloxy group having 6 to 30 carbon atoms, m is each independently an integer of 1 to 6, and p is each independently 0 or 1 and n is an integer of 1 to 4.)
[2]
The compound according to [1], wherein the compound represented by the formula (1) is a compound represented by the following formula (1A-2).

(In the formula (1A-2), R ¹ and p are the same as described above, R ⁶ has the same meaning as R ² described in the formula (1), and each m ⁶ independently represents 1 to 3 Is an integer.)
[3]
The compound according to [1], wherein the compound represented by the formula (1) is a compound represented by the following formula (1B-2).

(In formula (1B-2), R ¹ and p are as defined above, R ⁶ has the same meaning as R ² described in formula (1), and m ⁶ is independently 1 to 3 Is an integer.)
[4]
The compound according to [2], wherein the compound represented by the formula (1A-2) is a compound represented by the following formula (BisN-1-CH1) or the following formula (BisN-1-CH2).

[5]
The compound according to [2], wherein the compound represented by the formula (1A-2) is a compound represented by the following formula (BisN-1-PH1) or the following formula (BisN-1-PH2).

[6]
[1] A resin obtained by using the compound according to any one of [1] to [5] as a monomer.
[7]
The resin according to claim 6, which is obtained by reacting the compound according to any one of [1] to [5] with a compound having a crosslinking reactivity.
[8]
The crosslinking reactive compound is at least one selected from the group consisting of aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanates and unsaturated hydrocarbon group-containing compounds. [7] Resin.
[9]
Resin as described in [6] containing the structure represented by following formula (2).

(In the formula (2), each X independently represents an oxygen atom, a sulfur atom, or a non-bridged group, and R ¹ is a single bond or a 2n-valent group having 1 to 30 carbon atoms. Each may have an alicyclic hydrocarbon group, a double bond, a hetero atom or an aryl group having 6 to 30 carbon atoms, and each R ² is independently a straight chain having 1 to 10 carbon atoms. A branched or cyclic alkyl group, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, or a hydroxyl group, Here, at least one of R ² is an alkoxy group having 1 to 30 carbon atoms or an aryloxy group having 6 to 30 carbon atoms, and each R ³ is independently a single bond or a straight chain having 1 to 20 carbon atoms. a Jo or branched alkylene group, m ² are each independently 1 to Of integers, p is independently 0 or 1, n is an integer of 1-4.)
[10]
The resin according to [9], wherein the resin having a structure represented by the formula (2) is a resin having a structure represented by the following formula (2A).

(In formula (2A), R ¹ , R ² , R ³ , m ² , p and n are the same as described above.)
[11]
The resin according to [9], wherein the resin having a structure represented by the formula (2) is a resin having a structure represented by the following formula (2B).

(In formula (2B), R ¹ , R ² , R ³ , m ² , p and n are the same as described above.)
[12]
A material for forming an underlayer film for lithography, comprising the compound according to any one of [1] to [5] and / or the resin according to any one of claims 6 to 11.
[13]
The underlayer film forming material for lithography according to [12], further comprising an organic solvent.
[14]
The underlayer film forming material for lithography according to [12] or [13], further containing an acid generator.
[15]
The material for forming an underlayer film for lithography according to any one of [12] to [14], further comprising a crosslinking agent.
[16]
[12] A lithography lower layer film formed from the lithography lower layer film forming material according to any one of [15] to [15].
[17]
A step (A-1) of forming a lower layer film on the substrate using the lower layer film forming material for lithography described in any one of [12] to [15];
Forming at least one photoresist layer on the lower layer film (A-2);
After the step (A-2), a step of irradiating a predetermined region of the photoresist layer with radiation and developing (A-3);
A resist pattern forming method comprising:
[18]
A step (B-1) of forming a lower layer film on the substrate using the lower layer film forming material for lithography described in any one of [12] to [15];
Forming an intermediate layer film on the lower layer film using a resist intermediate layer film material containing silicon atoms (B-2);
Forming at least one photoresist layer on the intermediate film (B-3);
After the step (B-3), a step (B-4) of irradiating a predetermined region of the photoresist layer with radiation and developing to form a resist pattern;
After the step (B-4), the intermediate layer film is etched using the resist pattern as a mask, the lower layer film is etched using the obtained intermediate layer film pattern as an etching mask, and the obtained lower layer film pattern is etched. Forming a pattern on the substrate by etching the substrate as a mask (B-5);
A circuit pattern forming method.
[19]
A solution (A) containing an organic solvent which is not arbitrarily miscible with water, and the compound according to any one of [1] to [5] or the resin according to any one of [6] to [11] And a step of bringing the aqueous solution into contact with an acidic aqueous solution for extraction.

According to the present invention, a compound that is useful for forming a photoresist underlayer film, is applicable to a wet process, has excellent heat resistance and etching resistance, and has further improved solubility in a safe solvent, A resin and a material for forming a lower layer film for lithography can be realized.

Hereinafter, an embodiment of the present invention (hereinafter referred to as the present embodiment) will be described. In addition, this embodiment is an illustration for demonstrating this invention, and this invention is not limited only to this embodiment.

[Compound]
The compound of this embodiment is represented by the following formula (1).

(In the formula (1), each X independently represents an oxygen atom or a sulfur atom, or non-bridged, and R ¹ is a single bond or a 2n-valent group having 1 to 30 carbon atoms, Each may have an alicyclic hydrocarbon group, a double bond, a hetero atom, or an aryl group having 6 to 30 carbon atoms, and each R ² is independently a straight chain having 1 to 10 carbon atoms, A branched or cyclic alkyl group, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, or a hydroxyl group, And at least one of R ² is an alkoxy group having 1 to 30 carbon atoms or an aryloxy group having 6 to 30 carbon atoms, m is each independently an integer of 1 to 6, and p is each independently 0 or 1 and n is an integer of 1 to 4.)

Since it has the above structure, the compound of this embodiment is useful for forming a photoresist underlayer film, can be applied to a wet process, has excellent heat resistance and etching resistance, and is soluble in a safe solvent. Is further improved. In addition, it can be said that the compound of this embodiment has high heat resistance, a relatively high carbon concentration, a relatively low oxygen concentration, and a high solvent solubility because of its structural characteristics. When a compound having such a predetermined structure is used as a material for forming an underlayer film for lithography, the deterioration of the film during high-temperature baking is suppressed, and an underlayer film having excellent etching resistance against oxygen plasma etching or the like can be formed. Furthermore, since the adhesiveness with the resist layer is also excellent, an excellent resist pattern can be obtained.

In the above formula (1), each X independently represents an oxygen atom, a sulfur atom, or no bridge. Here, the case where X is non-crosslinked means that the compound represented by the formula (1) is a compound represented by the following formula (1B).

(In formula (1B), R ¹ , R ² , m, p and n are the same as described above.)

R ¹ is a single bond or a 2n-valent group having 1 to 30 carbon atoms. The compound of the present embodiment has a configuration in which each benzene ring is bonded via R ¹ . Here, the 2n-valent group may have an alicyclic hydrocarbon group, a double bond, a hetero atom, or an aryl group having 6 to 30 carbon atoms.

R ² is independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 1 to It is a monovalent group selected from the group consisting of 30 alkoxy groups, aryloxy groups having 6 to 30 carbon atoms, and hydroxyl groups, and m bonds to each aromatic ring. Here, at least one of R ² is an alkoxy group having 1 to 30 carbon atoms or an aryloxy group having 6 to 30 carbon atoms.

M is an integer of 1 to 6 independently. Each p is independently 0 or 1. n is an integer of 1 to 4.

The 2n-valent group is an alkylene group having 1 to 30 carbon atoms when n = 1, an alkanetetrayl group having 1 to 30 carbon atoms when n = 2, and a carbon number when n = 3. An alkanehexyl group having 2 to 30 carbon atoms, and when n = 4, an alkaneoctyl group having 3 to 30 carbon atoms. Examples of the 2n-valent group include those having a linear, branched or cyclic structure.

The 2n-valent group may have an alicyclic hydrocarbon group, a double bond, a hetero atom, or an aryl group having 6 to 30 carbon atoms. Here, the alicyclic hydrocarbon group includes a bridged alicyclic hydrocarbon group.

Further, the alkoxy group having 1 to 30 carbon atoms is selected from a linear hydrocarbon group, a branched hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group consisting of a combination of two or more thereof. And a group composed of an oxygen atom. Here, the alicyclic hydrocarbon group includes a bridged alicyclic hydrocarbon group. The alkoxy group may have a double bond, a hetero atom, or a halogen atom.

The alkoxy group having 1 to 30 carbon atoms is not particularly limited, but is preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group. Group, cyclohexenyloxy group, isophoronyloxy group, norbornanyloxy group, adamantyloxy group, tricyclodecanyloxy group, pyridinyloxy group, phenyloxy group, methylphenyloxy group, dimethylphenyloxy group, ethylphenyloxy Group, fluorophenyloxy group, chlorophenyloxy group, bromophenyloxy group, iodophenyloxy group, hydroxyphenyloxy group, methoxyphenyloxy group, aminophenyloxy group, nitrophenyloxy group, shear Phenyloxy group, phenylphenyloxy group, phenyloxyphenyloxy group, naphthyloxy group, methylnaphthyloxy group, dimethylnaphthyloxy group, ethylnaphthyloxy group, fluoronaphthyloxy group, chloronaphthyloxy group, bromonaphthyloxy group, iodo Naphtyloxy group, hydroxynaphthyloxy group, methoxynaphthyloxy group, aminonaphthyloxy group, nitronaphthyloxy group, cyanonaphthyloxy group, phenylnaphthyloxy group, phenyloxynaphthyloxy group, anthracenyloxy group, pyrenyloxy group, fullyl Olenyloxy group, more preferably cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cyclohexenyloxy group, isophoronyloxy group, norborna Ruoxy group, adamantyloxy group, tricyclodecanyloxy group, pyridinyloxy group, phenyloxy group, methylphenyloxy group, dimethylphenyloxy group, ethylphenyloxy group, fluorophenyloxy group, chlorophenyloxy group, bromophenyloxy group, Iodophenyloxy group, hydroxyphenyloxy group, methoxyphenyloxy group, aminophenyloxy group, nitrophenyloxy group, cyanophenyloxy group, phenylphenyloxy group, phenyloxyphenyloxy group, naphthyloxy group, methylnaphthyloxy group, Dimethylnaphthyloxy, ethylnaphthyloxy, fluoronaphthyloxy, chloronaphthyloxy, bromonaphthyloxy, iodonaphthyloxy, hydroxynaphthyloxy Xyl, methoxynaphthyloxy, aminonaphthyloxy, nitronaphthyloxy, cyanonaphthyloxy, phenylnaphthyloxy, phenyloxynaphthyloxy, anthracenyloxy, pyrenyloxy, fluorenyloxy More preferably, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cyclohexenyloxy group, isophoronyloxy group, norbornanyloxy group, adamantyloxy group, tricyclodecanyloxy group, pyridinyloxy group, phenyl Oxy group, methylphenyloxy group, dimethylphenyloxy group, ethylphenyloxy group, methoxyphenyloxy group, phenylphenyloxy group, phenyloxyphenyloxy group, naphthyloxy group, methylna Tyloxy group, dimethylnaphthyloxy group, ethylnaphthyloxy group, methoxynaphthyloxy group, phenylnaphthyloxy group, phenyloxynaphthyloxy group, anthracenyloxy group, pyrenyloxy group, fluorenyloxy group, particularly preferably Examples thereof include a cyclohexyloxy group and a phenyloxy group.

The aryloxy group having 6 to 30 carbon atoms is a group composed of an aromatic hydrocarbon group having 6 to 30 carbon atoms and an oxygen atom, and contributes to improving the solubility of the compound represented by the formula (1). Specific examples of such an aryloxy group having 6 to 30 carbon atoms include, but are not limited to, phenyloxy group, methylphenyloxy group, dimethylphenyloxy group, trimethylphenyloxy group, ethylphenyloxy group, propylphenyl group Oxy group, butylphenyloxy group, cyclohexylphenyloxy group, biphenyloxy group, terphenyloxy group, naphthyloxy group, fluorenyloxy group, anthracyloxy group, pyrenyloxy group, methylpyrenyloxy group, dimethylpyrenyloxy group Groups and the like.

The compound represented by the formula (1) has a relatively low molecular weight, but has high heat resistance due to the rigidity of its structure, and therefore can be used under high temperature baking conditions. In addition, since the substrate has a relatively low molecular weight and low viscosity, it is easy to uniformly fill every corner of a step even on a substrate having a step (particularly, a fine space or a hole pattern). As a result, the material for forming a lower layer film for lithography using this tends to have a relatively advantageous improvement in embedding characteristics and planarization characteristics. Moreover, since it is a compound having a relatively high carbon concentration, high etching resistance is also imparted. Furthermore, having an alkoxy group having 1 to 30 carbon atoms further improves the solubility in a safe solvent for highly stabilizing the product quality.

Here, the compound represented by the formula (1) is preferably a compound represented by the following formula (1A) from the viewpoint of improving heat resistance by forming a rigid structure.

In the formula (1A), R ¹ , R ² , m, p and n are the same as described above.

In addition, the compound represented by the formula (1) is preferably a compound represented by the following formula (1B) from the viewpoint of improving the safety solvent solubility.

In the formula (1B), R ¹ , R ² , m, p and n are the same as described above.

The compound represented by the formula (1A) is more preferably a compound represented by the formula (1A-1) from the viewpoint of improving the heat resistance by improving the degree of crosslinking during baking by introducing an R ⁵ O group.

(In formula (1A-1), each R ⁴ independently represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 2 to 10 carbon atoms. R ⁵ is a monovalent group having 1 to 30 carbon atoms, and is a linear hydrocarbon group, branched hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group And a monovalent group consisting of a combination of two or more thereof, which may have a double bond, a hetero atom, or a halogen atom, wherein the alicyclic hydrocarbon group As for, a bridged alicyclic hydrocarbon group is also included, wherein m ₃ is each independently an integer of 0 to 4, where at least one m ₃ is 1 and m ₄ is each independently And m ₃ + m ₄ is an integer of 1 to 4, and R ¹ , n and p are the same as above. Like.)

The compound represented by the formula (1B) is more preferably a compound represented by the formula (1B-1) from the viewpoint of further improving the solubility of the safe solvent by introducing the R ⁵ O group. .

(In formula (1B-1), R ¹ , R ⁴ , R ⁵ , m ³ , m ⁴ , n and p are the same as described above.)

From the viewpoint of low molecular weight, the compound represented by the formula (1) is an embodiment in which n = 1 in the formula (1), that is, a compound represented by the following formula (1-2). preferable.

In the formula (1-2), X, R ¹ and p have the same meanings as those explained in the formula (1), R ⁶ has the same meaning as R ² explained in the formula (1), m ⁶ is an integer of 1 to 3.

In addition, the compound represented by the formula (1-2) is an embodiment in which X═O in the formula (1-2), that is, the following formula (1A-2), from the viewpoint of improving heat resistance by forming a rigid structure. It is more preferable that it is a compound represented by these.

In the formula (1A-2), R ¹ and p have the same meanings as described in the formula (1). R ⁶ has the same meaning as R ² described in Formula (1), and m ⁶ is an integer of 1 to 3.

In addition, from the viewpoint of improving the safety solvent solubility, the compound represented by the formula (1-2) is an embodiment in which X is non-crosslinked in the formula (1-2), that is, in the following formula (1B-2) More preferably, it is a compound represented.

In the formula (1B-2), R ¹ and p have the same meanings as described in the formula (1). R ⁶ has the same meaning as R ² described in Formula (1), and m ⁶ is an integer of 1 to 3.

From the viewpoint of combining solubility and heat resistance, the compound represented by the above formula (1A-2) is preferably a compound represented by the following formula (1A-3).

In the formula (1A-3), R ¹ has the same meaning as described in the formula (1), and R ⁵ has the same meaning as that described in the formula (1A-1).

From the viewpoint of combining solubility and heat resistance, the compound represented by the above formula (1B-2) is preferably a compound represented by the following formula (1B-3).

In the formula (1B-3), R ¹ has the same meaning as described in the formula (1), and R ⁵ has the same meaning as described in the formula (1A-1).

Specific examples of the compound represented by the formula (1) are illustrated below, but are not limited to those listed here.

In the above formula, R ² , X and m are as defined in the above formula (1).

Specific examples of the compound represented by the formula (1) are further exemplified below, but are not limited to those listed here.

In the above formula, X has the same meaning as described in the formula (1), and R ⁵ has the same meaning as described in the formula (1A-1).

From the viewpoint of solubility, the compound represented by the formula (1A-2) may be a compound represented by the following formula (BisN-1-CH1) or the following formula (BisN-1-CH2). Particularly preferred.

From the viewpoint of solubility, the compound represented by the formula (1A-2) may be a compound represented by the following formula (BisN-1-PH1) or the following formula (BisN-1-PH2). preferable.

The compound represented by the formula (1) can be appropriately synthesized by applying a known technique, and the synthesis technique is not particularly limited. For example, under normal pressure, a phenol or thiophenol corresponding to the desired compound structure and an aldehyde or ketone corresponding to the desired compound structure are subjected to a polycondensation reaction in the presence of an acid catalyst. A compound represented by the formula (1) can be obtained. Moreover, it can also carry out under pressure as needed. By changing the reaction conditions, it is possible to control the generation ratio between the structure when X is crosslinked and the structure when X is non-crosslinked. For example, when the reaction temperature is increased, the reaction time is increased, and the acid strength of the acid catalyst is increased, the generation ratio of the structure crosslinked with X tends to increase. On the other hand, when the reaction temperature is lowered, the reaction time is shortened, and the acid strength of the acid catalyst is weakened, the generation ratio of the structure that is non-crosslinked with X tends to increase. When emphasizing high solvent solubility, a higher ratio of the structure when X is non-crosslinked is preferable, while when emphasizing high heat resistance, a higher ratio of the structure when crosslinked with X is preferable. .

Examples of the phenols include, but are not limited to, phenol, methylphenol, methoxybenzene, catechol, resorcinol, hydroquinone, and the like. These can be used individually by 1 type or in combination of 2 or more types. Among these, it is more preferable to use hydroquinone because a xanthene structure can be easily formed.

Examples of the thiophenols include, but are not particularly limited to, benzenethiol, methylbenzenethiol, methoxybenzenethiol, benzenedithiol, and the like. These can be used individually by 1 type or in combination of 2 or more types. Among these, it is more preferable to use benzenedithiol because a thioxanthene structure can be easily formed.

Examples of the aldehydes include formaldehyde, trioxane, paraformaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, hexylaldehyde, decylaldehyde, undecylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, fluorobenzaldehyde, Chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, dimethylbenzaldehyde, ethylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarboxaldehyde, phenanthrenecarboxaldehyde, pyrene Examples include ruboxaldehyde, glyoxal, glutaraldehyde, phthalaldehyde, naphthalene dicarboxyaldehyde, biphenyl dicarboxaldehyde, bis (diformylphenyl) methane, bis (diformylphenyl) propane, and benzenetricarboxaldehyde. There is no particular limitation. These can be used individually by 1 type or in combination of 2 or more types. Among these, benzaldehyde, hydroxybenzaldehyde, fluorobenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, dimethylbenzaldehyde, ethylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarboxaldehyde, phenanthrenecarboxaldehyde , Pyrenecarboxaldehyde, glyoxal, glutaraldehyde, phthalaldehyde, naphthalene dicarboxyaldehyde, biphenyl dicarboxaldehyde, anthracene dicarboxaldehyde, bis (diformylphenyl) methane, bis (diformylphenyl) propane, benzene It is preferred from the viewpoint of giving high heat resistance to use a tri-carboxaldehyde.

Examples of the ketones include acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, and the like. However, it is not particularly limited to these. These can be used alone or in combination of two or more. Among these, it is preferable to use cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone and anthraquinone from the viewpoint of giving high heat resistance.

The acid catalyst used in the above reaction can be appropriately selected from known ones and is not particularly limited. As such an acid catalyst, inorganic acids and organic acids are widely known, and specific examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, oxalic acid, Malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfone Acids, organic acids such as naphthalene sulfonic acid, naphthalene disulfonic acid, Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride, silicotungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid However, it is not particularly limited to these. Among these, an organic acid and a solid acid are preferable from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferably used from the viewpoint of production such as availability and ease of handling. In addition, about an acid catalyst, 1 type can be used individually or in combination of 2 or more types. The amount of the acid catalyst used can be appropriately set according to the raw material used, the type of catalyst used, and the reaction conditions, and is not particularly limited, but is 0.01 to 100 per 100 parts by mass of the reactive raw material. It is preferable that it is a mass part.

In the above reaction, a reaction solvent may be used. The reaction solvent is not particularly limited as long as the reaction between the aldehyde or ketone to be used and the phenol or thiophenol proceeds, and can be appropriately selected from known ones. , Water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, or a mixed solvent thereof. In addition, a solvent can be used individually by 1 type or in combination of 2 or more types. Moreover, the usage-amount of these solvent can be suitably set according to the raw material to be used, the kind of acid catalyst to be used, and also reaction conditions. The amount of the solvent used is not particularly limited, but is preferably in the range of 0 to 2000 parts by mass with respect to 100 parts by mass of the reaction raw material. Furthermore, the reaction temperature in the above reaction can be appropriately selected according to the reactivity of the reaction raw materials. The reaction temperature is not particularly limited, but is usually in the range of 10 to 200 ° C. In order to form a xanthene structure or a thioxanthene structure as the compound represented by the general formula (1) of the present embodiment, the reaction temperature is preferably higher, and specifically in the range of 60 to 200 ° C. The reaction method can be appropriately selected from known methods, and is not particularly limited. However, the reaction method may be a method in which phenols or thiophenols, aldehydes or ketones, and an acid catalyst are charged all at once, phenols or thiols. There is a method in which phenols, aldehydes or ketones are dropped in the presence of an acid catalyst. After completion of the polycondensation reaction, the obtained compound can be isolated according to a conventional method, and is not particularly limited. For example, in order to remove unreacted raw materials, acid catalysts, etc. existing in the system, a general technique such as raising the temperature of the reaction kettle to 130 to 230 ° C. and removing volatile components at about 1 to 50 mmHg, By taking it, the target compound can be obtained.

As preferable reaction conditions, 1 mol to excess of phenols or thiophenols and 0.001 to 1 mol of acid catalyst are used with respect to 1 mol of aldehyde or ketone, and 50 to 150 ° C. at normal pressure. The reaction proceeds for about 20 minutes to 100 hours.

After completion of the reaction, the target product can be isolated by a known method. For example, the reaction solution is concentrated, pure water is added to precipitate the reaction product, cooled to room temperature, filtered and separated, and the solid obtained by filtration is dried, followed by column chromatography. Separating and purifying from the by-product, and performing solvent distillation, filtration, and drying, a compound that is a precursor of the compound represented by the formula (1), which is the target product, can be obtained.

The precursor compound obtained by the above method can be obtained by a known method, for example, by replacing the hydrogen atom of at least one phenolic hydroxyl group with a monovalent group having 1 to 30 carbon atoms. A compound represented by the formula (1) can be obtained.

The method for replacing the hydrogen atom of the phenolic hydroxyl group with a monovalent group having 1 to 30 carbon atoms is not particularly limited. For example, the precursor compound is reacted with a halogenated hydrocarbon compound in the presence of a base catalyst. Can be obtained by dehydrohalogenation reaction.

The halogenated hydrocarbon compound is not particularly limited, but a halogenated hydrocarbon compound having 1 to 30 carbon atoms is preferably used. The halogenated hydrocarbon compound is composed of a linear hydrocarbon group, a branched hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a group composed of two or more thereof, and a halogen atom. Here, the alicyclic hydrocarbon group includes a bridged cyclic hydrocarbon group. The halogenated hydrocarbon compound may have a double bond, a hetero atom, or another type of halogen atom.

Examples of the halogenated hydrocarbon compound include methyl chloride, methyl bromide, methyl iodide, propyl chloride, propyl bromide, propyl iodide, butyl chloride, butyl bromide, butyl iodide, heptyl chloride, heptyl bromide, Examples include heptyl iodide, hexyl chloride, hexyl bromide, hexyl iodide, decyl chloride, decyl bromide, decyl iodide, or a compound group represented by the following formula (5), but are not particularly limited thereto. These can be used individually by 1 type or in combination of 2 or more types.

In the formula (5), Y represents a chlorine atom, a bromine atom or an iodine atom.

In the presence of a base catalyst (sodium carbonate, potassium carbonate, triethylamine, ammonia, sodium hydroxide, etc.) in an organic solvent such as dimethylformamide, 0.1 to 10 halogenated hydrocarbon compounds are used per 1 mol of the precursor compound. The mole is reacted at 0 to 150 ° C. for about 0.5 to 20 hours. By this reaction, at least one phenolic hydroxyl group in the obtained precursor compound can be converted into an alkoxyl group. Next, the compound represented by the formula (1) is obtained by filtration, washing with alcohols such as methanol, washing with water, separation by filtration, and drying.

The molecular weight of the compound represented by the formula (1) is not particularly limited, but the weight average molecular weight Mw is preferably 350 to 5,000, and more preferably 400 to 3,000. In addition, said Mw can be measured by the method as described in the Example mentioned later.

[resin]
The compound represented by the formula (1) can be used as it is as a material for forming a lower layer film for lithography. Moreover, it can be used also as resin obtained by using the compound represented by said Formula (1) as a monomer. For example, it can also be used as a resin obtained by reacting a compound represented by the formula (1) with a compound having crosslinking reactivity. Examples of the resin obtained using the compound represented by the formula (1) as a monomer include those having a structure represented by the following formula (2). That is, the lower layer film forming material for lithography of the present embodiment may contain a resin having a structure represented by the following formula (2).

(In the formula (2), each X independently represents an oxygen atom or a sulfur atom, or non-bridged, R ¹ is a single bond or a 2n-valent group having 1 to 30 carbon atoms, The hydrogen group may have an alicyclic hydrocarbon group, a double bond, a hetero atom, or an aryl group having 6 to 30 carbon atoms, and each R ² is independently a straight chain having 1 to 10 carbon atoms. A chain, branched or cyclic alkyl group, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, or a hydroxyl group. Wherein at least one of R ² is an alkoxy group having 1 to 30 carbon atoms or an aryloxy group having 6 to 30 carbon atoms, and each R ³ independently represents a single bond or 1 to 20 carbon atoms. a linear or branched alkylene group, m ² are each independently Is an integer from 1 to 5, p are each independently 0 or 1, n is an integer of 1-4.)

In the formula (2), each X independently represents an oxygen atom, a sulfur atom, or no crosslinking. Here, the case where X is non-crosslinked means that the structure represented by the formula (2) is a structure represented by the following formula (2B).

(In formula (2B), R ¹ , R ² , R ³ , m ² , n and p are the same as described above.)

In the formula (2), R ¹ is a single bond or a 2n-valent group having 1 to 30 carbon atoms, and each aromatic ring is bonded through this R ¹ . Here, the 2n-valent group may have an alicyclic hydrocarbon group, a double bond, a hetero atom, or an aryl group having 6 to 30 carbon atoms.

R ² each independently represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 1 to 30 carbon atoms. A monovalent group selected from the group consisting of an alkoxy group having 5 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms and a hydroxyl group, each having m ² bonded to the aromatic ring. Here, at least one of R ² is an alkoxy group having 1 to 30 carbon atoms or an aryloxy group having 6 to 30 carbon atoms.

Each R ³ is independently a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms.

m ² is each independently an integer of 1 to 5, p is each independently 0 or 1, and n is an integer of 1 to 4. The 2n-valent group has the same meaning as described in the description relating to the formula (1).

Here, the structure represented by the formula (2) is preferably a structure represented by the following formula (2A) from the viewpoint of improving heat resistance by forming a rigid structure.

(In formula (2A), R ¹ , R ² , R ³ , m ² , n and p are the same as described above.)

Here, the structure represented by the formula (2A) is a structure represented by the following formula (2A-1) from the viewpoint of improving heat resistance by improving the degree of crosslinking during baking by introducing an R ⁵ O group. Is preferred.

(In the formula (2A-1), R ¹ , R ⁴ , R ⁵ , m ³ , m ⁴ , n and p are the same as described above.)

In addition, the structure represented by the formula (2B) is preferably a structure represented by the following formula (2B-1) from the viewpoint of improving the safety solvent solubility.

(In the formula (2B-1), R ¹ , R ⁴ , R ⁵ , m ³ , m ⁴ , n and p are the same as above.)

The crosslinkable compound is not particularly limited as long as it can oligomerize the compound represented by the formula (1), and a known compound can be used. Specific examples thereof include, but are not limited to, aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanates, unsaturated hydrocarbon group-containing compounds, and the like.

Specific examples of the resin having the structure represented by the formula (2) are not limited to the following, but the compound represented by the formula (1) is condensed with an aldehyde which is a compound having a crosslinking reactivity, and the like. And a novolak resin.

Here, as an aldehyde used when novolak-forming the compound represented by the formula (1), for example, formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, Examples thereof include, but are not limited to, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, and furfural. Among these, formaldehyde is preferable. In addition, these aldehydes can be used individually by 1 type or in combination of 2 or more types. The amount of the aldehyde used is not particularly limited, but is preferably 0.2 to 5 mol, more preferably 0.5 to 2 mol, relative to 1 mol of the compound represented by the formula (1). is there.

In the condensation reaction between the compound represented by the formula (1) and the aldehyde, an acid catalyst can be used. The acid catalyst used here can be appropriately selected from known ones and is not particularly limited. As such an acid catalyst, inorganic acids and organic acids are widely known, and specific examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, oxalic acid, Malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfone Acids, organic acids such as naphthalene sulfonic acid, naphthalene disulfonic acid, Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride, silicotungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid However, it is not particularly limited to these. Among these, organic acids and solid acids are preferable from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferable from the viewpoint of production such as availability and ease of handling. In addition, about an acid catalyst, 1 type can be used individually or in combination of 2 or more types. The amount of the acid catalyst used can be appropriately set according to the raw material to be used, the type of the acid catalyst to be used, and the reaction conditions, and is not particularly limited, but is 0.01 to 100 parts by weight with respect to 100 parts by mass of the reaction raw material. The amount is preferably 100 parts by mass. Indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborna-2-ene, α-pinene, β-pinene In the case of a copolymerization reaction with a compound having a non-conjugated double bond such as limonene, aldehydes may not be used.

In the condensation reaction between the compound represented by the formula (1) and the aldehyde, a reaction solvent can also be used. The reaction solvent in this polycondensation can be appropriately selected from known solvents and is not particularly limited. Examples thereof include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, and mixed solvents thereof. Can be mentioned. In addition, a solvent can be used individually by 1 type or in combination of 2 or more types.

Also, the amount of these solvents used can be appropriately set according to the raw material used, the type of acid catalyst used, and the reaction conditions. The amount of the solvent used is not particularly limited, but is preferably in the range of 0 to 2000 parts by mass with respect to 100 parts by mass of the reaction raw material.

Furthermore, the reaction temperature can be appropriately selected according to the reactivity of the reaction raw material, and is not particularly limited. The reaction temperature is usually in the range of 10 to 200 ° C. In addition, the reaction method can select and use a well-known method suitably, Although it does not specifically limit, The method of charging the compound represented by said Formula (1), aldehydes, and a catalyst collectively, said Formula (1) There is a method in which a compound or an aldehyde represented by (2) is dropped in the presence of a catalyst. After completion of the polycondensation reaction, the obtained compound can be isolated according to a conventional method, and is not particularly limited. For example, in order to remove unreacted raw materials, catalysts, etc. existing in the system, a general method such as raising the temperature of the reaction vessel to 130 to 230 ° C. and removing volatile components at about 1 to 50 mmHg is adopted. As a result, a novolak resin as the target product can be obtained.

Here, the resin having the structure represented by the formula (2) may be a homopolymer of the compound represented by the formula (1), but is a copolymer with other phenols. May be. Examples of the copolymerizable phenols include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, resorcinol, methylresorcinol, catechol, butylcatechol, methoxyphenol, methoxyphenol, Although propylphenol, pyrogallol, thymol, etc. are mentioned, it is not specifically limited to these.

Further, the resin having the structure represented by the formula (2) may be copolymerized with a polymerizable monomer in addition to the other phenols described above. Examples of the copolymerization monomer include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene. , Norbornadiene, vinylnorbornaene, pinene, limonene and the like, but are not particularly limited thereto. The resin having the structure represented by the above formula (2) is a binary or more (for example, 2-4 quaternary) copolymer of the compound represented by the above formula (1) and the above-described phenols. Even if it is a binary or more (for example, 2-4 quaternary) copolymer of the compound represented by the formula (1) and the above-mentioned copolymerization monomer, it is represented by the formula (1). It may be a ternary or more (for example, ternary to quaternary) copolymer of the above compound, the above-mentioned phenols, and the above-mentioned copolymerization monomer.

The molecular weight of the resin having the structure represented by the formula (2) is not particularly limited, but the polystyrene equivalent weight average molecular weight (Mw) is preferably 500 to 30,000, more preferably 750 to 20,000. Further, from the viewpoint of increasing the crosslinking efficiency and suppressing the volatile components in the baking, the molecular weight of the resin having the structure represented by the formula (2) is such that the dispersity (weight average molecular weight Mw / number average molecular weight Mn) is 1. Those within the range of 2 to 7 are preferred.

The compound represented by the formula (1) and / or the resin having the structure represented by the formula (2) has high solubility in a solvent from the viewpoint of easier application of a wet process. It is preferable. More specifically, these compounds and / or resins preferably have a solubility in 1-methoxy-2-propanol (PGME) or propylene glycol monomethyl ether acetate (PGMEA) of 10% by mass or more. Here, the solubility with respect to PGME or PGMEA is defined as “the mass of the compound and / or resin ÷ (the mass of the compound and / or the resin + the mass of the solvent) × 100 (mass%)”. For example, it is evaluated that 10 g of the compound and / or resin is dissolved in 90 g of PGMEA when the solubility of the compound and / or resin in PGMEA is “10% by mass or more” and is not dissolved. The case where the solubility is “less than 10% by mass”.

[Underlayer film forming material for lithography]
The material for forming a lower layer film for lithography of the present embodiment contains at least one substance selected from the group consisting of the compound of the present embodiment and the resin of the present embodiment. More specifically, the material for forming a lower layer film for lithography of the present embodiment is obtained by reacting the compound represented by the formula (1) and the compound represented by the formula (1) with a compound having a crosslinking reaction. It contains at least one substance selected from the group consisting of resins.

When the material for forming a lower layer film for lithography of the present embodiment includes an organic solvent which is an optional component described later, the content of the compound of the present embodiment and / or the resin of the present embodiment is not particularly limited, but includes an organic solvent. The total amount is preferably 1 to 33 parts by mass, more preferably 2 to 25 parts by mass, and still more preferably 3 to 20 parts by mass with respect to 100 parts by mass.

The underlayer film forming material for lithography of the present embodiment may contain other components such as a crosslinking agent, an acid generator, and an organic solvent, as necessary. Hereinafter, these optional components will be described.

[Crosslinking agent]
The lower layer film forming material for lithography of the present embodiment may contain a crosslinking agent as necessary from the viewpoint of suppressing intermixing. Specific examples of the crosslinking agent that can be used in this embodiment include double bonds such as melamine compounds, guanamine compounds, glycoluril compounds or urea compounds, epoxy compounds, thioepoxy compounds, isocyanate compounds, azide compounds, alkenyl ether groups, and the like. Examples of the compound include those substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, but are not particularly limited thereto. In addition, these crosslinking agents can be used individually by 1 type or in combination of 2 or more types. These may be used as additives, but these crosslinkable groups may be introduced as pendant groups in the polymer side chain. A compound containing a hydroxy group can also be used as a crosslinking agent.

Specific examples of the melamine compound include, but are not limited to, hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexa Examples include acyloxymethyl melamine, compounds in which 1 to 6 methylol groups of hexamethylol melamine are acyloxymethylated, or a mixture thereof. Specific examples of the epoxy compound include, but are not limited to, tris (2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylolethane triglycidyl ether, and the like. .

Specific examples of the guanamine compound include, but are not limited to, a compound in which 1 to 4 methylol groups of tetramethylolguanamine, tetramethoxymethylguanamine, and tetramethylolguanamine are methoxymethylated, or a mixture thereof, tetramethoxyethylguanamine, tetra Examples include compounds in which 1 to 4 methylol groups of acyloxyguanamine and tetramethylolguanamine are acyloxymethylated, or a mixture thereof. Specific examples of the glycoluril compound include, but are not limited to, a compound in which 1 to 4 methylol groups of tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethylglycoluril, tetramethylolglycoluril are methoxymethylated or Examples thereof include a mixture thereof, a compound in which 1 to 4 methylol groups of tetramethylol glycoluril are acyloxymethylated, or a mixture thereof. Specific examples of the urea compound include, but are not limited to, tetramethylol urea, tetramethoxymethyl urea, a compound in which 1 to 4 methylol groups of tetramethylol urea are methoxymethylated, or a mixture thereof, tetramethoxyethyl urea, and the like. Can be mentioned.

Specific examples of the compound containing an alkenyl ether group include, but are not limited to, ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol. Divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane And trivinyl ether.

In the lower layer film forming material for lithography of the present embodiment, the content of the crosslinking agent is not particularly limited, but is 5 to 50 with respect to 100 parts by mass of the compound of the present embodiment and / or the resin of the present embodiment. The amount is preferably part by mass, more preferably 10 to 40 parts by mass. By setting it as the above preferable range, the occurrence of the mixing phenomenon with the resist layer tends to be suppressed, the antireflection effect is enhanced, and the film forming property after crosslinking tends to be enhanced.

[Acid generator]
The lower layer film forming material for lithography of the present embodiment may contain an acid generator as necessary from the viewpoint of further promoting the crosslinking reaction by heat. In the industry, as an acid generator, those that generate acid by thermal decomposition and those that generate acid by light irradiation are known, and any of them can be used.

As an acid generator,
1) Onium salts of the following general formula (P1a-1), (P1a-2), (P1a-3) or (P1b)
2) a diazomethane derivative of the following general formula (P2),
3) a glyoxime derivative of the following general formula (P3),
4) A bissulfone derivative of the following general formula (P4),
5) A sulfonic acid ester of an N-hydroxyimide compound of the following general formula (P5),
6) β-ketosulfonic acid derivative,
7) a disulfone derivative,
8) Nitrobenzyl sulfonate derivative,
9) Examples thereof include, but are not particularly limited to, sulfonic acid ester derivatives. In addition, these acid generators can be used individually by 1 type or in combination of 2 or more types.

In the above formula, R ^101a , R ^101b and R ^101c are each independently a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, and 6 to 6 carbon atoms. 20 aryl groups, aralkyl groups having 7 to 12 carbon atoms, or aryloxoalkyl groups, part or all of hydrogen atoms of these groups may be substituted with alkoxy groups or the like. R ^101b and R ^101c may form a ring. When a ring is formed, R ^101b and R ^101c each independently represent an alkylene group having 1 to 6 carbon atoms. K ⁻ represents a non-nucleophilic counter ion. R ^101d , R ^101e , R ^101f and R ^101g are each independently represented by adding a hydrogen atom to R ^101a , R ^101b and R ^101c . R ^101d and R ^101e , R ^101d and R ^101e and R ^101f may form a ring, and in the case of forming a ring, R ^101d and R ^101e and R ^101d , R ^101e and R ^101f have 3 carbon atoms. Represents a alkylene group of ˜10, or a heteroaromatic ring having a nitrogen atom in the formula in the ring.

R ^101a , R ^101b , R ^101c , R ^101d , R ^101e , R ^101f and R ^101g may be the same as or different from each other. Specific examples of the alkyl group include, but are not limited to, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group. , Heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group, adamantyl group and the like. Examples of alkenyl groups include, but are not limited to, vinyl groups, allyl groups, propenyl groups, butenyl groups, hexenyl groups, and cyclohexenyl groups. Examples of the oxoalkyl group include, but are not limited to, 2-oxocyclopentyl group, 2-oxocyclohexyl group, 2-oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2- An oxoethyl group, a 2- (4-methylcyclohexyl) -2-oxoethyl group, and the like can be given. Examples of the oxoalkenyl group include, but are not limited to, a 2-oxo-4-cyclohexenyl group, a 2-oxo-4-propenyl group, and the like. Examples of the aryl group include, but are not limited to, phenyl group, naphthyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group. An alkoxyphenyl group such as m-tert-butoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, Alkylphenyl groups such as dimethylphenyl group, alkyl naphthyl groups such as methyl naphthyl group and ethyl naphthyl group, alkoxy naphthyl groups such as methoxy naphthyl group and ethoxy naphthyl group, dialkyl naphthyl groups such as dimethyl naphthyl group and diethyl naphthyl group, dimethoxy naphthyl group Group, diethoxynaphthy Dialkoxy naphthyl group such as a group. Although not limited to the following as an aralkyl group, For example, a benzyl group, a phenylethyl group, a phenethyl group etc. are mentioned. Examples of aryloxoalkyl groups include, but are not limited to, 2-phenyl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group, and the like. And 2-aryl-2-oxoethyl group. Examples of the non-nucleophilic counter ion of K ⁻ include, but are not limited to, halide ions such as chloride ion and bromide ion, triflate, 1,1,1-trifluoroethanesulfonate, nonafluorobutanesulfonate, and the like. Fluoroalkyl sulfonates, tosylate, benzene sulfonate, 4-fluorobenzene sulfonate, aryl sulfonates such as 1,2,3,4,5-pentafluorobenzene sulfonate, and alkyl sulfonates such as mesylate and butane sulfonate.

In addition, when R ^101d , R ^101e , R ^101f , and R ^101g are heteroaromatic rings having a nitrogen atom in the formula, the heteroaromatic ring is not limited to the following, but an imidazole derivative ( For example, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, pyrroline derivatives (eg pyrroline, 2-methyl-1-pyrroline etc.), pyrrolidine derivatives (eg pyrrolidine, N-methyl) Pyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethyl) Pyridine, triethylpi Gin, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine Derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (eg quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnori Derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives , Uracil derivatives, uridine derivatives and the like.

The onium salts of the formulas (P1a-1) and (P1a-2) have a function as a photoacid generator and a thermal acid generator. The onium salt of the formula (P1a-3) has a function as a thermal acid generator.

In the formula (P1b), R ^102a and R ^102b each independently represent a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. R ¹⁰³ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. R ^104a and R ^104b each independently represent a 3-oxoalkyl group having 3 to 7 carbon atoms. K ⁻ represents a non-nucleophilic counter ion.

Specific examples of R ^102a and R ^102b include, but are not limited to, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. A heptyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a cyclopropylmethyl group, a 4-methylcyclohexyl group, a cyclohexylmethyl group, and the like. Specific examples of R ¹⁰³ include, but are not limited to, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, 1,4-cyclohexylene. Group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, 1,4-cyclooctylene group, 1,4-cyclohexanedimethylene group and the like. Specific examples of R ^104a and R ^104b include, but are not limited to, 2-oxopropyl group, 2-oxocyclopentyl group, 2-oxocyclohexyl group, 2-oxocycloheptyl group and the like. K ^- is the formula (P1a-1), can be exemplified the same ones as described in (P1a-2) and (P1a-3).

In the formula (P2), R ¹⁰⁵ and R ¹⁰⁶ are each independently a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms or halogen. An aryl group or an aralkyl group having 7 to 12 carbon atoms.

Examples of the alkyl group for R ¹⁰⁵ and R ¹⁰⁶ include, but are not limited to, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl. Group, heptyl group, octyl group, amyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, norbornyl group, adamantyl group and the like. Examples of the halogenated alkyl group include, but are not limited to, a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, and a nonafluorobutyl group. Examples of the aryl group include, but are not limited to, phenyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert- Alkoxyphenyl groups such as butoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, dimethylphenyl group, etc. An alkylphenyl group is mentioned. Examples of the halogenated aryl group include, but are not limited to, a fluorophenyl group, a chlorophenyl group, a 1,2,3,4,5-pentafluorophenyl group, and the like. Examples of the aralkyl group include, but are not limited to, a benzyl group and a phenethyl group.

In the formula (P3), R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ are each independently a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, or aryl having 6 to 20 carbon atoms. A group, a halogenated aryl group, or an aralkyl group having 7 to 12 carbon atoms; R ¹⁰⁸ and R ¹⁰⁹ may be bonded to each other to form a cyclic structure. When forming a cyclic structure, R ¹⁰⁸ and R ¹⁰⁹ each represent a linear or branched alkylene group having 1 to 6 carbon atoms. .

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group, and aralkyl group of R ¹⁰⁷ , R ¹⁰⁸ , and R ¹⁰⁹ include the same groups as those described for R ¹⁰⁵ and R ¹⁰⁶ . The alkylene group for R ¹⁰⁸ and R ¹⁰⁹ is not limited to the following, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group.

(In formula (P4), R ^101a and R ^101b are the same as above.)

In the formula (P5), R ¹¹⁰ represents an arylene group having 6 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms, or an alkenylene group having 2 to 6 carbon atoms, and part or all of the hydrogen atoms of these groups May further be substituted with a linear or branched alkyl group or alkoxy group having 1 to 4 carbon atoms, a nitro group, an acetyl group, or a phenyl group. R ¹¹¹ represents a linear, branched or substituted alkyl group, alkenyl group, alkoxyalkyl group, phenyl group, or naphthyl group having 1 to 8 carbon atoms, and some or all of the hydrogen atoms of these groups are further An alkyl group or alkoxy group having 1 to 4 carbon atoms; a phenyl group optionally substituted with an alkyl group, alkoxy group, nitro group or acetyl group having 1 to 4 carbon atoms; a heteroaromatic group having 3 to 5 carbon atoms; Alternatively, it may be substituted with a chlorine atom or a fluorine atom.

Here, the arylene group of R ¹¹⁰ is not limited to the following, and examples thereof include a 1,2-phenylene group and a 1,8-naphthylene group. Examples of the alkylene group include, but are not limited to, methylene group, ethylene group, trimethylene group, tetramethylene group, phenylethylene group, norbornane-2,3-diyl group, and the like. Examples of the alkenylene group include, but are not limited to, 1,2-vinylene group, 1-phenyl-1,2-vinylene group, 5-norbornene-2,3-diyl group, and the like. ^Examples of the alkyl group for R ¹¹¹ include the same groups as R ^101a to R ^101c . Examples of the alkenyl group include, but are not limited to, vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 3-butenyl group, isoprenyl group, 1-pentenyl group, 3-pentenyl group, 4-pentenyl group. Group, dimethylallyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 3-heptenyl group, 6-heptenyl group, 7-octenyl group and the like. Examples of the alkoxyalkyl group include, but are not limited to, for example, methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, pentyloxymethyl group, hexyloxymethyl group, heptyloxymethyl group, methoxyethyl group, Ethoxyethyl group, propoxyethyl group, butoxyethyl group, pentyloxyethyl group, hexyloxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, butoxypropyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, A methoxypentyl group, an ethoxypentyl group, a methoxyhexyl group, a methoxyheptyl group, etc. are mentioned.

Further, the optionally substituted alkyl group having 1 to 4 carbon atoms is not limited to the following, but for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert- A butyl group etc. are mentioned. Examples of the alkoxy group having 1 to 4 carbon atoms include, but are not limited to, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, and tert-butoxy group. Examples of the phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a nitro group, or an acetyl group include, but are not limited to, for example, a phenyl group, a tolyl group, a p-tert-butoxyphenyl group , P-acetylphenyl group, p-nitrophenyl group and the like. Examples of the heteroaromatic group having 3 to 5 carbon atoms include, but are not limited to, a pyridyl group and a furyl group.

Specific examples of the acid generator include, but are not limited to, tetramethylammonium trifluoromethanesulfonate, tetramethylammonium nonafluorobutanesulfonate, triethylammonium nonafluorobutanesulfonate, pyridinium nonafluorobutanesulfonate, triethyl camphorsulfonate Ammonium, pyridinium camphorsulfonate, tetra-n-butylammonium nonafluorobutanesulfonate, tetraphenylammonium nonafluorobutanesulfonate, tetramethylammonium p-toluenesulfonate, diphenyliodonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p- tert-butoxyphenyl) phenyliodonium, p-toluenesulfonic acid diphenyliodonium P-toluenesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid bis (p-tert- Butoxyphenyl) phenylsulfonium, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfone Bis (p-tert-butoxyphenyl) phenylsulfonium acid, Tris (p-tert-butoxyphenyl) p-toluenesulfonate Phonium, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, p-toluene Cyclohexylmethyl (2-oxocyclohexyl) sulfonium sulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trifluoromethanesulfonic acid Trinaphthylsulfonium Cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, trifluoromethanesulfonate (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium, ethylenebis [methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfonate], Onium salts such as 1,2'-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (Cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, Bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane, bis (isoamylsulfonyl) diazomethane, Bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane, 1- diazomethane derivatives such as tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane, bis- (p-toluenesulfonyl) -α-dimethyl group Oxime, bis- (p-toluenesulfonyl) -α-diphenylglyoxime, bis- (p-toluenesulfonyl) -α-dicyclohexylglyoxime, bis- (p-toluenesulfonyl) -2,3-pentanedione glyoxime, Bis- (p-toluenesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis- (n-butanesulfonyl) -α-dimethylglyoxime, bis- (n-butanesulfonyl) -α-diphenylglyoxime Oxime, bis- (n-butanesulfonyl) -α-dicyclohexylglyoxime, bis- (n-butanesulfonyl) -2,3-pentanedione glyoxime, bis- (n-butanesulfonyl) -2-methyl-3, 4-Pentanedione glyoxime, bis- (methanesulfonyl) -α-dimethylglyoxy Shim, bis- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis- (tert-butanesulfonyl) -α-dimethylglyoxime Oxime, bis- (perfluorooctanesulfonyl) -α-dimethylglyoxime, bis- (cyclohexanesulfonyl) -α-dimethylglyoxime, bis- (benzenesulfonyl) -α-dimethylglyoxime, bis- (p-fluorobenzene) Sulfonyl) -α-dimethylglyoxime, bis- (p-tert-butylbenzenesulfonyl) -α-dimethylglyoxime, bis- (xylenesulfonyl) -α-dimethylglyoxime, bis- (camphorsulfonyl) -α-dimethyl Glyoximes such as glyoximes Conductors, bissulfone derivatives such as bisnaphthylsulfonylmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane, bisbenzenesulfonylmethane, Β-ketosulfone derivatives such as 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane, 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane, disulfone derivatives such as diphenyldisulfone derivatives, dicyclohexyldisulfone derivatives, p- Nitrobenzyl sulfonate derivatives such as 2,6-dinitrobenzyl toluenesulfonate, 2,4-dinitrobenzyl p-toluenesulfonate, Sulfonic acid ester derivatives such as 1,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy) benzene, N- Hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide ethanesulfonate, N-hydroxysuccinimide 1-propanesulfonate, N-hydroxysuccinimide 2-propanesulfonate, N- Hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide 1-octanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfone Esters, N-hydroxysuccinimide p-methoxybenzenesulfonate, N-hydroxysuccinimide 2-chloroethanesulfonate, N-hydroxysuccinimidebenzenesulfonate, N-hydroxysuccinimide-2,4,6-trimethylbenzenesulfonate N-hydroxysuccinimide 1-naphthalenesulfonic acid ester, N-hydroxysuccinimide 2-naphthalenesulfonic acid ester, N-hydroxy-2-phenylsuccinimide methanesulfonic acid ester, N-hydroxymaleimide methanesulfonic acid ester, N-hydroxymaleimide ethane Sulfonic acid ester, N-hydroxy-2-phenylmaleimide methanesulfonic acid ester, N-hydroxyglutarimide meta Sulfonate, N-hydroxyglutarimide benzenesulfonate, N-hydroxyphthalimide methanesulfonate, N-hydroxyphthalimide benzenesulfonate, N-hydroxyphthalimide trifluoromethanesulfonate, N-hydroxyphthalimide p-toluenesulfone Acid ester, N-hydroxynaphthalimide methanesulfonate, N-hydroxynaphthalimide benzenesulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide methanesulfonate, N-hydroxy-5-norbornene -2,3-dicarboximide trifluoromethanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide p-to Sulfonic acid ester derivatives of N- hydroxy imide compounds such as toluenesulfonic acid esters.
Among these, in particular, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, p-toluenesulfonic acid Triphenylsulfonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, trifluoromethanesulfonic acid trinaphthylsulfonium, trifluoromethanesulfonic acid cyclohexylmethyl (2-oxocyclohexyl) sulfonium, trifluoromethanesulfonic acid (2-norbornyl) methyl (2-oxocyclohexyl) Sil) sulfonium, onium salts such as 1,2'-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n- Diazomethane derivatives such as butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, Glyoxime derivatives such as bis- (p-toluenesulfonyl) -α-dimethylglyoxime and bis- (n-butanesulfonyl) -α-dimethylglyoxime; Bissulfone derivatives such as naphthylsulfonylmethane, N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide 1-propanesulfonate, N-hydroxysuccinimide 2-propanesulfonate, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, N-hydroxynaphthalimide benzenesulfonic acid ester, etc. Acid ester derivatives are preferably used.

In the material for forming a lower layer film for lithography of the present embodiment, the content of the acid generator is not particularly limited, but the content of the compound of the present embodiment and / or the resin of the present embodiment is 0.1 parts by mass. The amount is preferably 1 to 50 parts by mass, and more preferably 0.5 to 40 parts by mass. By setting the amount within the above preferable range, the amount of acid generated tends to increase and the crosslinking reaction tends to be enhanced, and the occurrence of a mixing phenomenon with the resist layer tends to be suppressed.

Furthermore, the material for forming a lower layer film for lithography according to the present embodiment may contain a basic compound from the viewpoint of improving storage stability.

The basic compound serves as a quencher for the acid to prevent the acid generated in a trace amount from the acid generator from causing the crosslinking reaction to proceed. Examples of such basic compounds include primary, secondary or tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, A nitrogen-containing compound having a sulfonyl group, a nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative, and the like are exemplified, but not limited thereto.

Specific examples of primary aliphatic amines include, but are not limited to, ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, Examples include pentylamine, tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like. Specific examples of secondary aliphatic amines include, but are not limited to, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, Dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyl Examples include tetraethylenepentamine. Specific examples of tertiary aliphatic amines include, but are not limited to, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine , Tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ′, N ′ -Tetramethylmethylenediamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyltetraethylenepentamine and the like.

Specific examples of the hybrid amines include, but are not limited to, dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine, and the like. Specific examples of aromatic amines and heterocyclic amines include, but are not limited to, aniline derivatives (for example, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2 -Methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitro Aniline, 3,5-dinitroaniline, N, N-dimethyltoluidine, etc.), diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (eg pyrrole, 2H-pyrrole) , 1-methyl Rolls, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (eg oxazole, isoxazole etc.), thiazole derivatives (eg thiazole, isothiazole etc.), imidazole derivatives (eg imidazole) 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, pyrroline derivatives (eg pyrroline, 2-methyl-1-pyrroline etc.), pyrrolidine derivatives (eg pyrrolidine, N-methylpyrrolidine, etc.) Pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) ) Pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl- 2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, Pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (eg quinolin derivatives) , 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline Derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

Further, specific examples of nitrogen-containing compounds having a carboxy group include, but are not limited to, aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (for example, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine). Glycylleucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine) and the like. Specific examples of the nitrogen-containing compound having a sulfonyl group include, but are not limited to, 3-pyridinesulfonic acid, pyridinium p-toluenesulfonate, and the like. Specific examples of the nitrogen-containing compound having a hydroxyl group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound include, but are not limited to, 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3- Indolemethanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino- 1-propanol, 4-amino-1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2- Hydroxyethoxy) ethyl] Perazine, piperidine ethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyurolidine, 3-cuincridinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) iso And nicotinamide. Specific examples of amide derivatives include, but are not limited to, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like. . Specific examples of the imide derivative include, but are not limited to, phthalimide, succinimide, maleimide and the like.

In the lower layer film forming material for lithography of the present embodiment, the content of the basic compound is not particularly limited, but is 0.001 to 2 with respect to 100 parts by mass of the compound of the present embodiment and / or the resin of the present embodiment. It is preferably part by mass, more preferably 0.01 to 1 part. By making it into the above preferred range, the storage stability tends to be enhanced without excessively impairing the crosslinking reaction.

[Organic solvent]
The material for forming a lower layer film for lithography of the present embodiment may contain an organic solvent. Any known organic solvent can be used as long as it can dissolve at least the compound of this embodiment and / or the resin of this embodiment.
Specific examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, ethyl lactate, methyl acetate, ethyl acetate and butyl acetate. Ester solvents such as isoamyl acetate, ethyl lactate, methyl methoxypropionate and methyl hydroxyisobutyrate, alcohol solvents such as methanol, ethanol, isopropanol and 1-ethoxy-2-propanol, aromatics such as toluene, xylene and anisole Examples thereof include, but are not limited to, hydrocarbons. These organic solvents can be used individually by 1 type or in combination of 2 or more types.

Among the above organic solvents, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl hydroxyisobutyrate, and anisole are particularly preferable from the viewpoint of safety.

The content of the organic solvent is not particularly limited, but is 100 to 10,000 parts by mass with respect to 100 parts by mass of the compound of the present embodiment and / or the resin of the present embodiment from the viewpoint of solubility and film formation. The amount is preferably 200 to 5,000 parts by mass.

[Other ingredients]
Further, the material for forming a lower layer film for lithography of the present embodiment may contain other resins and / or compounds for the purpose of imparting thermosetting properties and controlling absorbance. Examples of such other resins and / or compounds include naphthol resins, xylene resins, naphthol-modified resins, phenol-modified resins of naphthalene resins, polyhydroxystyrene, dicyclopentadiene resins, (meth) acrylates, dimethacrylates, trimethacrylates, tetra Resins containing no heterocyclic ring or aromatic ring such as methacrylate, vinyl naphthalene, polyacenaphthylene and other naphthalene rings, phenanthrenequinone, biphenyl rings such as fluorene, hetero rings having hetero atoms such as thiophene and indene; rosin resins; Examples thereof include resins or compounds containing an alicyclic structure such as cyclodextrin, adamantane (poly) ol, tricyclodecane (poly) ol, and derivatives thereof, but are not particularly limited thereto. Furthermore, the lower layer film forming material for lithography of the present embodiment may contain a known additive, for example, an ultraviolet absorber, a surfactant, a colorant, a nonionic surfactant and the like.

[Liquid lower layer film and multilayer resist pattern forming method]
The lower layer film for lithography of this embodiment is formed from the lower layer film forming material for lithography of this embodiment.

The resist pattern forming method of the present embodiment includes a step (A-1) of forming a lower layer film on a substrate using the lower layer film forming material for lithography of the present embodiment, and at least on the lower layer film. A step (A-2) of forming a single photoresist layer, and a step (A-3) of developing after irradiating a predetermined region of the photoresist layer with radiation after the step (A-2) And having.

Furthermore, the circuit pattern forming method of this embodiment includes a step (B-1) of forming a lower layer film on a substrate using the lower layer film forming material for lithography of the present embodiment, and a silicon film on the lower layer film. An intermediate layer film forming step using a resist intermediate layer film material containing atoms (B-2), and a step of forming at least one photoresist layer on the intermediate layer film (B-3); After the step (B-3), a predetermined region of the photoresist layer is irradiated with radiation and developed to form a resist pattern (B-4), and after the step (B-4), The intermediate layer film is etched using the resist pattern as a mask, the lower layer film is etched using the obtained intermediate layer film pattern as an etching mask, and the substrate is etched using the obtained lower layer film pattern as an etching mask. Having a step (B-5) to form a pattern on a substrate with a.

The formation method of the underlayer film for lithography of the present embodiment is not particularly limited as long as it is formed from the above-described material for forming an underlayer film for lithography, and a known method can be applied. For example, after applying the lower layer film forming material for lithography described above onto a substrate by a known coating method such as spin coating or screen printing or a printing method, the lower layer film is removed by evaporating an organic solvent or the like. Can be formed. At the time of forming the lower layer film, baking is preferably performed in order to suppress the occurrence of the mixing phenomenon with the upper layer resist and to promote the crosslinking reaction. In this case, the baking temperature is not particularly limited, but is preferably in the range of 80 to 450 ° C., more preferably 200 to 400 ° C. Also, the baking time is not particularly limited, but is preferably within the range of 10 to 300 seconds. The thickness of the lower layer film can be appropriately selected according to the required performance and is not particularly limited, but is usually preferably about 30 to 20,000 nm, more preferably 50 to 15,000 nm. It is preferable. After the formation of the lower layer film, in the case of a two-layer process, a silicon-containing resist layer thereon or a single-layer resist made of ordinary hydrocarbons, in the case of a three-layer process, a silicon-containing intermediate layer is further formed thereon It is preferable to produce a single-layer resist layer that does not contain silicon. In this case, a well-known thing can be used as a photoresist material for forming this resist layer.

After forming the lower layer film on the substrate, in the case of a two-layer process, a silicon-containing resist layer or a single layer resist made of normal hydrocarbon is formed on the lower layer film, and in the case of a three-layer process, a silicon-containing layer is formed on the lower layer film. A single-layer resist layer not containing silicon can be formed on the intermediate layer and further on the silicon-containing intermediate layer. In these cases, the photoresist material for forming the resist layer can be appropriately selected from known materials and is not particularly limited.

As a silicon-containing resist material for a two-layer process, from the point of resistance to oxygen gas etching, a silicon atom-containing polymer such as a polysilsesquioxane derivative or a vinylsilane derivative is used as a base polymer, and an organic solvent, an acid generator, If necessary, a positive photoresist material containing a basic compound or the like is preferably used. Here, as the silicon atom-containing polymer, a known polymer used in this type of resist material can be used.

As the silicon-containing intermediate layer for the three-layer process, a polysilsesquioxane-based intermediate layer is preferably used. By providing the intermediate layer with an effect as an antireflection film, reflection tends to be effectively suppressed. For example, in a 193 nm exposure process, if a material containing many aromatic groups and having high substrate etching resistance is used as the lower layer film, the k value increases and the substrate reflection tends to increase, but by suppressing the reflection in the intermediate layer, The substrate reflection can be reduced to 0.5% or less. As the intermediate layer having such an antireflection effect, polysilsesquioxane crosslinked with acid or heat into which a light absorbing group having a phenyl group or a silicon-silicon bond is introduced is preferably used for 193 nm exposure.

Also, an intermediate layer formed by a Chemical-Vapor-deposition (CVD) method can be used. The intermediate layer having a high effect as an antireflection film produced by the CVD method is not limited to the following, but for example, a SiON film is known. In general, the formation of the intermediate layer by a wet process such as spin coating or screen printing has a simpler and more cost-effective advantage than the CVD method. The upper layer resist in the three-layer process may be either a positive type or a negative type, and the same one as a commonly used single layer resist can be used.

Furthermore, the lower layer film of this embodiment can also be used as an antireflection film for a normal single layer resist or a base material for suppressing pattern collapse. Since the lower layer film of this embodiment is excellent in etching resistance for the base processing, it can be expected to function as a hard mask for the base processing.

In the case of forming a resist layer from the photoresist material, a wet process such as spin coating or screen printing is preferably used as in the case of forming the lower layer film. Further, after the resist material is applied by spin coating or the like, prebaking is usually performed, but this prebaking is preferably performed at 80 to 180 ° C. for 10 to 300 seconds. Then, according to a conventional method, a resist pattern can be obtained by performing exposure, post-exposure baking (PEB), and development. The thickness of the resist film is not particularly limited, but is generally preferably 30 to 500 nm, more preferably 50 to 400 nm.

Further, the exposure light may be appropriately selected and used according to the photoresist material to be used. In general, high energy rays having a wavelength of 300 nm or less, specifically, 248 nm, 193 nm, 157 nm excimer laser, 3 to 20 nm soft X-ray, electron beam, X-ray and the like can be mentioned.

The resist pattern formed by the above method is one in which pattern collapse is suppressed by the lower layer film of this embodiment. Therefore, by using the lower layer film of this embodiment, a finer pattern can be obtained, and the exposure amount necessary for obtaining the resist pattern can be reduced.

Next, etching is performed using the obtained resist pattern as a mask. Gas etching is preferably used as the etching of the lower layer film in the two-layer process. As gas etching, etching using oxygen gas is suitable. In addition to oxygen gas, an inert gas such as He or Ar, or CO, CO ₂ , NH ₃ , SO ₂ , N ₂ , NO _{2 or} H ₂ gas can be added. Further, it is possible to perform gas etching using only CO, CO ₂ , NH ₃ , N ₂ , NO _{2, and} H ₂ gas without using oxygen gas. In particular, the latter gas is used for side wall protection for preventing undercut of the pattern side wall. On the other hand, gas etching is also preferably used in the etching of the intermediate layer in the three-layer process. As the gas etching, the same one as described in the above two-layer process can be applied. In particular, the processing of the intermediate layer in the three-layer process is preferably performed using a fluorocarbon gas and a resist pattern as a mask. Thereafter, as described above, the lower layer film can be processed by, for example, oxygen gas etching using the intermediate layer pattern as a mask.

Here, when an inorganic hard mask intermediate layer film is formed as the intermediate layer, a silicon oxide film, a silicon nitride film, or a silicon oxynitride film (SiON film) is formed by a CVD method, an ALD method, or the like. The method for forming the nitride film is not limited to the following, and examples thereof include methods described in Japanese Patent Application Laid-Open No. 2002-334869 (Patent Document 6) and WO 2004/066377 (Patent Document 7).
A photoresist film can be formed directly on such an intermediate film, but an organic antireflection film (BARC) is formed on the intermediate film by spin coating, and a photoresist film is formed thereon. May be.

As the intermediate layer, an intermediate layer based on polysilsesquioxane is also preferably used. By providing the resist intermediate layer film as an antireflection film, reflection tends to be effectively suppressed. Specific materials of the polysilsesquioxane-based intermediate layer are not limited to the following, but are described, for example, in JP-A-2007-226170 (Patent Document 8) and JP-A-2007-226204 (Patent Document 9). The thing which was done is mentioned.

Etching of the next substrate can also be performed by a conventional method. For example, if the substrate is SiO ₂ or SiN, etching mainly using a chlorofluorocarbon gas, if p-Si, Al, or W is chlorine or bromine gas, Etching mainly composed of can be performed. When the substrate is etched with a chlorofluorocarbon gas, the silicon-containing resist of the two-layer resist process and the silicon-containing intermediate layer of the three-layer process are peeled off simultaneously with the substrate processing. On the other hand, when the substrate is etched with a chlorine-based or bromine-based gas, the silicon-containing resist layer or the silicon-containing intermediate layer is separately peeled, and generally, dry etching peeling with a chlorofluorocarbon-based gas is performed after the substrate is processed. .

The lower layer film of this embodiment is characterized by excellent etching resistance of these substrates.
A known substrate can be appropriately selected and used, and is not particularly limited. Examples thereof include Si, α-Si, p-Si, SiO ₂ , SiN, SiON, W, TiN, and Al. . The substrate may be a laminate having a film to be processed (substrate to be processed) on a base material (support). Examples of such processed films include various low-k films such as Si, SiO ₂ , SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, and Al-Si, and their stopper films. In general, a material different from the base material (support) is used. The thickness of the substrate to be processed or the film to be processed is not particularly limited, but is usually preferably about 50 to 10,000 nm, more preferably 75 to 5,000 nm.

[Method for purifying compound or resin]
In the purification method of the compound or resin in the present embodiment, an organic solvent that is not arbitrarily miscible with water and a solution (A) containing the compound of the present embodiment or the resin of the present embodiment are contacted with an acidic aqueous solution. An extracting step. Since it is comprised as mentioned above, according to the purification method of this embodiment, content of the various metals which can be contained as an impurity in the compound of this embodiment or the resin of this embodiment can be reduced.
More specifically, in this embodiment, the compound or the resin can be dissolved in an organic solvent that is not arbitrarily miscible with water, and the solution is further brought into contact with an acidic aqueous solution to perform the extraction treatment. Thus, after the metal component contained in the solution (A) is transferred to the aqueous phase, the organic phase and the aqueous phase are separated to reduce the metal content, thereby reducing the compound of the present embodiment or the resin of the present embodiment. Obtainable.

The compound of the present embodiment or the resin of the present embodiment may be used for the above purification alone, but two or more kinds may be mixed and used for the above purification. Moreover, the compound of this embodiment or the resin of this embodiment may contain various surfactants, various crosslinking agents, various acid generators, various stabilizers, and the like.

The organic solvent that is not arbitrarily miscible with water used in the present embodiment is not particularly limited, but is an organic solvent having a solubility in water of less than 30% at room temperature, more preferably less than 20%, Particularly preferred is an organic solvent that can be safely applied to a semiconductor manufacturing process of less than 10%. The amount of the organic solvent to be used is usually relative to the resin obtained by the reaction of the compound represented by the formula (1) or the compound represented by the formula (1) with a compound having a crosslinking reaction. About 1 to 100 times the mass is used.

Specific examples of the solvent used include, but are not limited to, ethers such as diethyl ether and diisopropyl ether, esters such as ethyl acetate, n-butyl acetate and isoamyl acetate, methyl ethyl ketone, methyl isobutyl ketone and ethyl isobutyl ketone. , Ketones such as cyclohexanone, cyclopentanone, 2-heptanone, 2-pentanone, glycols such as ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate Ether acetates, aliphatic hydrocarbons such as n-hexane and n-heptane, aromatic hydrocarbons such as toluene and xylene, methylene chloride, chlorine Halogenated hydrocarbons such as Holm and the like. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate and the like are preferable, methyl isobutyl ketone, ethyl acetate, cyclohexanone, propylene glycol monomethyl ether acetate are more preferable, More preferred are methyl isobutyl ketone and ethyl acetate. Methyl isobutyl ketone, ethyl acetate, and the like have a relatively high saturation solubility and a relatively low boiling point of the compound of the present embodiment or the resin of the present embodiment. It becomes possible to reduce the load in the.
These solvents can be used alone or in combination of two or more.

The acidic aqueous solution used in the present embodiment is appropriately selected from aqueous solutions in which generally known organic and inorganic compounds are dissolved in water. Although not limited to the following, for example, an aqueous solution in which a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or the like is dissolved in water, or acetic acid, propionic acid, succinic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid An aqueous solution in which an organic acid such as citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid or trifluoroacetic acid is dissolved in water. These acidic aqueous solutions can be used alone or in combination of two or more. Among these acidic aqueous solutions, one or more mineral acid aqueous solutions selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, or acetic acid, propionic acid, succinic acid, malonic acid, succinic acid, fumaric acid, maleic acid It is preferably an aqueous solution of one or more organic acids selected from the group consisting of acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid, sulfuric acid, nitric acid, and acetic acid, Aqueous solutions of carboxylic acids such as succinic acid, tartaric acid, and citric acid are more preferred, aqueous solutions of sulfuric acid, succinic acid, tartaric acid, and citric acid are more preferred, and aqueous solutions of succinic acid are even more preferred. Since polyvalent carboxylic acids such as succinic acid, tartaric acid, and citric acid are coordinated to metal ions to produce a chelate effect, it is considered that the metal tends to be removed more effectively. Moreover, it is preferable to use the water with low metal content, for example, ion-exchange water etc. according to the objective of this embodiment, as the water used here.

The pH of the acidic aqueous solution used in this embodiment is not particularly limited, but it is preferable to adjust the acidity of the aqueous solution in consideration of the influence on the compound of this embodiment or the resin of this embodiment. Normally, the pH range is about 0 to 5, preferably about 0 to 3.

The amount of acidic aqueous solution used in the present embodiment is not particularly limited, but from the viewpoint of reducing the number of extractions for metal removal and from the viewpoint of ensuring operability in consideration of the total amount of liquid, the amount used is It is preferable to adjust. From the above viewpoint, the amount of the aqueous solution used is usually 10 to 200% by mass, preferably 20 to 100% by mass with respect to the solution of the compound of the present embodiment or the resin of the present embodiment dissolved in an organic solvent. .

In the present embodiment, the metal component is extracted by bringing the acidic aqueous solution as described above into contact with the compound of the present embodiment or the resin of the present embodiment and a solution containing an organic solvent that is arbitrarily immiscible with water. be able to.

In this embodiment, it is preferable that the solution (A) further contains an organic solvent that is arbitrarily mixed with water. When an organic solvent arbitrarily mixed with water is included, the amount of the compound of the present embodiment or the resin of the present embodiment can be increased, the liquid separation property is improved, and purification can be performed with high pot efficiency. It tends to be possible. The method for adding an organic solvent arbitrarily mixed with water is not particularly limited. For example, any of a method of adding to a solution containing an organic solvent in advance, a method of adding to water or an acidic aqueous solution in advance, and a method of adding after bringing a solution containing an organic solvent into contact with water or an acidic aqueous solution may be used. Among these, the method of adding to the solution containing an organic solvent in advance is preferable from the viewpoint of the workability of the operation and the ease of management of the charged amount.

The organic solvent arbitrarily mixed with water used in the present embodiment is not particularly limited, but an organic solvent that can be safely applied to a semiconductor manufacturing process is preferable. The amount of the organic solvent arbitrarily mixed with the water to be used is not particularly limited as long as the solution phase and the aqueous phase are separated from each other. About 1 to 100 times the mass is used.

Specific examples of the solvent arbitrarily mixed with water used in the present embodiment include, but are not limited to, ethers such as tetrahydrofuran and 1,3-dioxolane, alcohols such as methanol, ethanol and isopropanol, acetone, Examples thereof include ketones such as N-methylpyrrolidone, and aliphatic hydrocarbons such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), and glycol ethers such as propylene glycol monoethyl ether. Among these, N-methylpyrrolidone, propylene glycol monomethyl ether and the like are preferable, and N-methylpyrrolidone and propylene glycol monomethyl ether are more preferable. These solvents can be used alone or in combination of two or more.

In the present embodiment, the temperature at the time of contacting the solution (A) with the acidic aqueous solution, that is, the extraction treatment is usually 20 to 90 ° C., and preferably 30 to 80 ° C. Although extraction operation is not specifically limited, For example, after mixing well by stirring etc., it is performed by leaving still. Thereby, the metal content contained in the solution containing the compound of the present embodiment or the resin of the present embodiment and the organic solvent is transferred to the aqueous phase. Moreover, the acidity of a solution falls by this operation, and the quality change of the compound of this embodiment or the resin of this embodiment can be suppressed.

Since the mixed solution is allowed to stand to separate into the compound of the present embodiment or the solution phase containing the resin of the present embodiment and an organic solvent and the aqueous phase, the compound of the present embodiment or the resin of the present embodiment is decanted or the like. And a solution containing the organic solvent is recovered. The standing time is not particularly limited, but it is preferable to adjust the standing time from the viewpoint of improving the separation between the solution phase containing the organic solvent and the aqueous phase. Usually, the time for standing is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer. The extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separation a plurality of times.

In the present embodiment, it is preferable to include a step of performing an extraction process with water after performing an extraction process by bringing the solution (A) into contact with an acidic aqueous solution. That is, after performing the above extraction process using an acidic aqueous solution, the solution containing the compound of this embodiment or the resin of this embodiment and the organic solvent extracted and recovered from the aqueous solution is further subjected to an extraction process with water. It is preferable to provide. The extraction treatment with water is not particularly limited. For example, the extraction treatment with water can be performed by mixing well by stirring and then allowing to stand. The solution obtained after the standing is separated into a solution phase and an aqueous phase containing the compound of the present embodiment or the resin of the present embodiment and an organic solvent, and an aqueous phase, and therefore the compound of the present embodiment or the resin of the present embodiment by decantation or the like. A solution phase containing an organic solvent can be recovered.
Moreover, it is preferable that the water used here is a thing with little metal content, for example, ion-exchange water etc. according to the objective of this embodiment. The extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separation a plurality of times. Further, the use ratio of both in the extraction process, conditions such as temperature and time are not particularly limited, but they may be the same as those in the contact process with the acidic aqueous solution.

The water that can be mixed into the compound of the present embodiment thus obtained or the solution containing the resin of the present embodiment and an organic solvent can be easily removed by performing an operation such as vacuum distillation. Moreover, an organic solvent can be added as needed, and the density | concentration of the compound of this embodiment or the resin of this embodiment can be adjusted to arbitrary density | concentrations.

The method of isolating the compound of the present embodiment or the resin of the present embodiment from the obtained compound of the present embodiment or the solution containing the resin of the present embodiment and an organic solvent is not particularly limited, and is removed under reduced pressure and reprecipitated. Can be carried out by a known method such as separation by, and combinations thereof. If necessary, known processes such as a concentration operation, a filtration operation, a centrifugal separation operation, and a drying operation can be performed.

Hereinafter, the present embodiment will be described in more detail with reference to synthesis examples and examples, but the present embodiment is not limited to these examples.

(Carbon concentration and oxygen concentration)
Carbon concentration and oxygen concentration (mass%) were measured by organic elemental analysis.
Apparatus: CHN coder MT-6 (manufactured by Yanaco Analytical Co., Ltd.)
(Molecular weight)
By GC-MS analysis, measurement was performed using Agilent 5975 / 6890N manufactured by Agilent. Alternatively, measurement was performed by LC-MS analysis using Water UP Acquity UPLC / MALDI-Synapt HDMS.
(Molecular weight measurement)
The molecular weight was determined by field desorption mass spectrometry (FD-MS) analysis.
(Molecular weight in terms of polystyrene)
The weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene were determined by gel permeation chromatography (GPC) analysis, and the degree of dispersion (Mw / Mn) was determined.
Apparatus: Shodex GPC-101 (manufactured by Showa Denko KK)
Column: KF-80M x 3
Eluent: THF 1mL / min
Temperature: 40 ° C
(Thermal decomposition temperature (Tg))
Using an EXSTAR6000DSC apparatus manufactured by SII Nanotechnology, about 5 mg of a sample was placed in an aluminum non-sealed container, and the temperature was increased to 500 ° C. at a temperature increase rate of 10 ° C./min in a nitrogen gas (30 mL / min) air stream. At that time, the temperature at which the reduced portion appeared in the baseline was defined as the thermal decomposition temperature (Tg), and the heat resistance was evaluated according to the following criteria.
Evaluation A: Thermal decomposition temperature is ≧ 150 ° C.
Evaluation C: Thermal decomposition temperature <150 ° C
(solubility)
At 23 ° C., the compound was dissolved in cyclohexanone (CHN) so as to be a 5 mass% solution, and then allowed to stand at 5 ° C. for 30 days. The results were evaluated according to the following criteria.
Evaluation A: Visually confirmed no deposit Evaluation C: Visually confirmed presence of deposit

(Synthesis Example 1) Synthesis of BisN-1 In a 1000 mL internal vessel equipped with a stirrer, a condenser tube and a burette, 16.0 g (100 mmol) of 2,6-naphthalenediol (Sigma-Aldrich reagent) and 4- Biphenyl aldehyde (Mitsubishi Gas Chemical Co., Ltd.) 18.2g (100mmol) and methyl isobutyl ketone 300mL were prepared, 95% sulfuric acid 50mL was added, and reaction was performed by stirring the reaction liquid at 100 degreeC for 6 hours. Next, the reaction solution was concentrated, 500 g of pure water was added to precipitate the reaction product, cooled to room temperature, and then filtered to separate. The solid obtained by filtration was dried and then separated and purified by column chromatography to obtain 30.5 g of the target compound (BisN-1) represented by the following formula.
The following peaks were found by 400 MHz-1H-NMR, and confirmed to have a chemical structure of the following formula. In addition, the substitution position of 2,6-dihydroxynaphthol was confirmed to be the 1st position because the signals of protons at the 3rd and 4th positions were doublets.
1H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 9.7 (2H, OH), 7.2 to 8.5 (19H, Ph—H), 6.6 (1H, C—H)

(Synthesis Example 1) Synthesis of BisN-1-CH1 and BisN-1-CH2 Into a 1000 mL container equipped with a stirrer, a condenser tube and a burette, 11.7 g (25 mmol) of BisN-1 obtained above was added. 108 g (810 mmol) of potassium carbonate and 200 mL of dimethylformamide were added, 250 g (1.53 mol) of bromocyclohexane was added, and the reaction was stirred at 110 ° C. for 24 hours to carry out the reaction. Next, the reaction solution was concentrated, 500 g of pure water was added to precipitate the reaction product, cooled to room temperature, and then filtered to separate. The obtained solid was filtered and dried, followed by separation and purification by column chromatography, whereby 2.4 g of the target compound (BisN-1-CH1) represented by the following formula and (BisN-1-CH2) 9.6 g was obtained.
About the obtained compound, when the NMR measurement was performed on the said measurement conditions, the following peaks were found and it confirmed that it had a chemical structure of a following formula.

BisN-1-CH1: δ (ppm) 9.7 (1H, OH), 7.2 to 8.5 (19H, Ph—H), 6.6 (1H, C—H), 1.4 ~ 4.5 (11H, Cy-H)
Here, Cy-H is a signal of the proton of the cyclohexyl group.

BisN-1-CH2: δ (ppm) 7.2 to 8.5 (19H, Ph—H), 6.6 (1H, C—H), 1.4 to 4.5 (22H, Cy—H)
Here, Cy-H is a signal of the proton of the cyclohexyl group.

The molecular weight of the obtained BisN-1-CH1 was 548. The carbon concentration was 85.3% by mass, and the oxygen concentration was 8.8% by mass.
The obtained BisN-1-CH2 had a molecular weight of 630. Moreover, carbon concentration was 85.7 mass% and oxygen concentration was 7.6 mass%.

(Synthesis Example 2) Synthesis of BisN-1-PH1 In a container having a volume of 1000 mL equipped with a stirrer, a condenser tube and a burette, 9.3 g (20 mmol) of BisN-1 obtained above and 26 g (80 mmol) of cesium carbonate were obtained. , 0.8 g (4 mmol) of copper iodide, 1.7 g (12 mmol) of dimethylglycine hydrochloride and 80 mL of dioxane, 8.2 g (40 mmol) of benzene iodide were added, and the reaction solution was stirred at 90 ° C. for 6 hours. The reaction was carried out with stirring. Next, 500 mL of ethyl acetate was added to precipitate the reaction product, which was cooled to room temperature and then separated by filtration. The obtained solid was filtered and dried, followed by separation and purification by column chromatography to obtain 7.2 g of the target compound (BisN-1-PH1) represented by the following formula.
About the obtained compound, when the NMR measurement was performed on the said measurement conditions, the following peaks were found and it confirmed that it had a chemical structure of a following formula.

BisN-1-PH1: δ (ppm) 9.2 (1H, OH), 6.7 to 7.8 (24H, Ph-H), 5.3 (1H, C—H)

(Synthesis Example 3) Synthesis of BisN-1-PH2 In a container having a volume of 1000 mL equipped with a stirrer, a condenser tube and a burette, 9.3 g (20 mmol) of BisN-1 obtained above and 26 g (80 mmol) of cesium carbonate were obtained. Then, 0.8 g (4 mmol) of copper iodide, 1.7 g (12 mmol) of dimethylglycine hydrochloride and 80 mL of dioxane were added, 8.2 g (40 mmol) of benzene iodide was added, and the reaction solution was stirred at 90 ° C. for 67 hours. The reaction was carried out with stirring. Next, 500 mL of ethyl acetate was added to precipitate the reaction product, which was cooled to room temperature and then separated by filtration. The obtained solid was filtered and dried, followed by separation and purification by column chromatography to obtain 6.8 g of the target compound (BisN-1-PH2) represented by the following formula.

BisN-1-PH2: δ (ppm) 6.8 to 8.0 (29H, Ph-H), 5.3 (1H, C—H)

The obtained BisN-1-PH1 had a molecular weight of 542. The carbon concentration was 86.3% by mass, and the oxygen concentration was 8.9% by mass.
The obtained BisN-1-PH2 had a molecular weight of 618. The carbon concentration was 87.4% by mass, and the oxygen concentration was 7.8% by mass.

(Production Example 1)
A 4-liter flask with an internal volume of 10 L, equipped with a Dimroth condenser, thermometer, and stirring blade and capable of bottoming out, was charged with 1.09 kg of 1,5-dimethylnaphthalene (7 mol, Mitsubishi Gas Chemical Co., Ltd.) in a nitrogen stream. ), 2.1 kg of 40% by weight formalin aqueous solution (28 mol as formaldehyde, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 0.97 ml of 98% by weight sulfuric acid (manufactured by Kanto Chemical Co., Ltd.), and refluxed at 100 ° C. under normal pressure. And allowed to react for 7 hours. Thereafter, 1.8 kg of ethylbenzene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) as a diluent solvent was added to the reaction solution, and after standing, the lower aqueous phase was removed. Further, neutralization and washing with water were carried out, and ethylbenzene and unreacted 1,5-dimethylnaphthalene were distilled off under reduced pressure to obtain 1.25 kg of a light brown solid dimethylnaphthalene formaldehyde resin.
The molecular weight of the obtained dimethylnaphthalene formaldehyde was Mn: 562, Mw: 1168, Mw / Mn: 2.08. Moreover, carbon concentration was 84.2 mass% and oxygen concentration was 8.3 mass%.

Thereafter, 100 g (0.51 mol) of dimethylnaphthalene formaldehyde resin obtained in Production Example 1 and paratoluene were added to a 0.5 L four-necked flask equipped with a Dimroth condenser, a thermometer and a stirring blade under a nitrogen stream. The sulfonic acid 0.05g was prepared, and it heated up to 190 degreeC, heated for 2 hours, and then stirred. Thereafter, 52.0 g (0.36 mol) of 1-naphthol was further added, and the temperature was further raised to 220 ° C. to react for 2 hours. After the solvent was diluted, neutralization and water washing were performed, and the solvent was removed under reduced pressure to obtain 126.1 g of a dark brown solid modified resin (CR-1).
The obtained resin (CR-1) was Mn: 885, Mw: 2220, and Mw / Mn: 4.17. The carbon concentration was 89.1% by mass, and the oxygen concentration was 4.5% by mass.

(Examples 1 to 4, Comparative Example 1)
The BisN-1-CH1, BisN-1-CH2, BisN-1-PH1, BisN-1-PH2, and BisN-1 were subjected to a heat resistance test and a solubility test. The results are shown in Table 1.
In addition, materials for forming a lower layer film for lithography having the composition shown in Table 1 were prepared. Next, these lower layer film-forming materials were spin-coated on a silicon substrate, and then baked at 240 ° C. for 60 seconds and further at 400 ° C. for 120 seconds to prepare lower layer films each having a thickness of 200 nm. The following were used about the acid generator, the crosslinking agent, and the organic solvent.
Acid generator: Ditertiary butyl diphenyliodonium nonafluoromethanesulfonate manufactured by Midori Kagaku Co. (denoted as “DTDPI” in the table)
Cross-linking agent: Nikalac MX270 manufactured by Sanwa Chemical Co., Ltd. (indicated in the table as “Nikalac”)
Organic solvent: cyclohexanone (indicated in the table as “CHN”)

[Etching test]
Furthermore, an etching test was performed under the conditions shown below to evaluate etching resistance. The evaluation results are shown in Table 1.
Etching device: RIE-10NR manufactured by Samco International
Output: 50W
Pressure: 20Pa
Time: 2min
Etching gas Ar gas flow rate: CF ₄ gas flow rate: O ₂ gas flow rate = 50: 5: 5 (sccm)
[Evaluation of etching resistance]
Etching resistance was evaluated according to the following procedure.
First, a novolac underlayer film was prepared under the same conditions as in Example 1 except that novolak (PSM4357 manufactured by Gunei Chemical Co., Ltd.) was used instead of the compound (BisN-1-CH1) used in Example 1. Then, the above-described etching test of the novolak underlayer film was performed, and the etching rate at that time was measured.
Next, the etching test of the lower layer film of Example 1 and Comparative Example 1 was similarly performed, and the etching rate at that time was measured.
Then, the etching resistance was evaluated according to the following evaluation criteria based on the etching rate of the novolak underlayer film. The results are shown in Table 1.
<Evaluation criteria>
A: Etching rate is less than -10% compared to the novolac lower layer film B: Etching rate is -10% to + 5% compared to the novolac lower layer film
C: Etching rate is more than + 5% compared to the novolak underlayer

Next, the materials for forming a lower layer film for lithography of Examples 1 to 4 and Comparative Example 1 containing BisN-1-CH1, BisN-1-CH2, BisN-1-PH1, BisN-1-PH2, and BisN-1 respectively Each solution was applied on a 300 nm thick SiO ₂ substrate and baked at 240 ° C. for 60 seconds and further at 400 ° C. for 120 seconds to form an underlayer film having a thickness of 80 nm. On this lower layer film, an ArF resist solution was applied and baked at 130 ° C. for 60 seconds to form a 150 nm-thick photoresist layer. As the ArF resist solution, a compound of the following formula (11): 5 parts by mass, triphenylsulfonium nonafluoromethanesulfonate: 1 part by mass, tributylamine: 2 parts by mass, and PGMEA: 92 parts by mass are blended. The prepared one was used.
The compound of the following formula (11) is 4.15 g of 2-methyl-2-methacryloyloxyadamantane, 3.00 g of methacryloyloxy-γ-butyrolactone, 2.08 g of 3-hydroxy-1-adamantyl methacrylate, azobisisobutyro 0.38 g of nitrile was dissolved in 80 mL of tetrahydrofuran, polymerized for 22 hours under a nitrogen atmosphere while maintaining the reaction temperature at 63 ° C., and then the reaction solution was dropped into 400 mL of n-hexane to give a product resin. Coagulated and purified, and the resulting white powder was filtered and dried overnight at 40 ° C. under reduced pressure.

(In the formula (11), 40, 40 and 20 indicate the ratio of each structural unit, and do not indicate a block copolymer.)

Next, the photoresist layer was subjected to mask exposure using an electron beam lithography apparatus (ELIONX, ELS-7500, 50 keV), baked at 115 ° C. for 90 seconds (PEB), and 2.38 mass% tetramethylammonium hydroxide. A positive resist pattern was obtained by developing with an aqueous solution of (TMAH) for 60 seconds.

Table 1 shows the results of observing the shapes and defects of the obtained 55 nm L / S (1: 1) and 80 nm L / S (1: 1) resist patterns.

(Comparative Example 2)
Except for using CR-1, it was carried out in the same manner as in Examples 1 to 4 and Comparative Example 1, and an underlayer film forming material was prepared and spin-coated on a silicon substrate, and then at 240 ° C. for 60 seconds and further at 400 ° C. Was baked for 120 seconds to prepare a lower layer film having a thickness of 200 nm. Thereafter, etching resistance was evaluated. The results are shown in Table 1.

(Comparative Example 3)
Except not forming the lower layer film, it was carried out in the same manner as in Examples 1 to 4 and Comparative Example 1, and a photoresist layer was directly formed on the SiO ₂ substrate to obtain a positive resist pattern. The evaluation results are shown in Table 1.

As is apparent from Table 1, Example 1 using BisN-1-CH1, which is a compound satisfying the configuration of the present embodiment, Example 2 using BisN-1-CH2, and BisN-1-PH1 were used. In Example 3 and Example 4 using BisN-1-PH2, it was confirmed that the heat resistance, solubility, and etching resistance were all good. On the other hand, in Comparative Example 1 using the polyphenol compound BisN-1, the heat resistance and etching resistance were good, but the solubility was poor. In Comparative Example 2 using CR-1 (phenol-modified dimethylnaphthalene formaldehyde resin (CR-1)), the etching resistance was poor.
In Examples 1 to 4, it was confirmed that the resist pattern shape after development was good and no defects were observed. On the other hand, in Comparative Example 1, it was confirmed that the resist pattern shape after development was poor and there were many defects. This is presumably because BisN-1 used in Comparative Example 1 has low solubility in the coating solvent.
Further, it was confirmed that Examples 1 to 4 were significantly superior in both resolution and sensitivity as compared with Comparative Example 3 in which the formation of the lower layer film was omitted.
From the difference in the resist pattern shape after development, it was shown that the lower layer film forming materials for lithography in Examples 1 to 4 had good adhesion to the resist material.

(Example 5)
The lower layer film forming material for lithography used in Example 1 was applied onto a 300 nm thick SiO ₂ substrate and baked at 240 ° C. for 60 seconds and further at 400 ° C. for 120 seconds, thereby forming a lower layer having a thickness of 80 nm. A film was formed. On this lower layer film, a silicon-containing intermediate layer material was applied and baked at 200 ° C. for 60 seconds to form an intermediate layer film having a thickness of 35 nm. Further, the ArF resist solution was applied on this intermediate layer film and baked at 130 ° C. for 60 seconds to form a 150 nm-thick photoresist layer. As the silicon-containing intermediate layer material, a silicon atom-containing polymer described in JP-A-2007-226170 <Synthesis Example 1> was used.
Next, the photoresist layer was subjected to mask exposure using an electron beam lithography apparatus (ELIONX, ELS-7500, 50 keV), baked at 115 ° C. for 90 seconds (PEB), and 2.38 mass% tetramethylammonium hydroxide. By developing with (TMAH) aqueous solution for 60 seconds, a positive resist pattern of 55 nm L / S (1: 1) was obtained.
Thereafter, using RIE-10NR manufactured by Samco International, the silicon-containing intermediate layer film (SOG) was dry-etched using the obtained resist pattern as a mask, and then the obtained silicon-containing intermediate layer film pattern was A dry etching process for the lower layer film using the mask and a dry etching process for the SiO ₂ film using the obtained lower layer film pattern as a mask were sequentially performed.

Each etching condition is as shown below.
Etching condition output to resist intermediate layer film of resist pattern : 50W
Pressure: 20Pa
Time: 1 min
Etching gas Ar gas flow rate: CF ₄ gas flow rate: O ₂ gas flow rate = 50: 8: 2 (sccm)
Output of etching condition to resist underlayer film of resist intermediate film pattern : 50W
Pressure: 20Pa
Time: 2min
Etching gas Ar gas flow rate: CF ₄ gas flow rate: O ₂ gas flow rate = 50: 5: 5 (sccm)
Etching condition output to SiO ₂ film of resist underlayer film pattern : 50W
Pressure: 20Pa
Time: 2min
Etching gas Ar gas flow rate: C ₅ F ₁₂ gas flow rate: C ₂ F ₆ gas flow rate: O ₂ gas flow rate = 50: 4: 3: 1 (sccm)

The pattern cross section (shape of the SiO ₂ film after etching) of Example 5 obtained as described above was observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd. As a result, it was confirmed that in Example 5 using the lower layer film satisfying the configuration of the present embodiment, the shape of the SiO ₂ film after etching in the multi-layer resist processing is rectangular, and no defects are observed, which is good. It was.

As described above, the present invention is not limited to the above-described embodiments and examples, and appropriate modifications can be made without departing from the scope of the invention.

This application is based on a Japanese patent application filed on December 25, 2014 (Japanese Patent Application No. 2014-262564), the contents of which are incorporated herein by reference.

Since the compounds and resins of the present invention have a relatively high carbon concentration, a relatively low oxygen concentration, a relatively high heat resistance, a high solvent solubility, and a wet process is applicable, these performances Can be used widely and effectively in various applications that require the Therefore, the present invention provides, for example, an electrical insulating material, a resist resin, a semiconductor sealing resin, an adhesive for printed wiring boards, an electrical laminate mounted on electrical equipment / electronic equipment / industrial equipment, etc.・ Matrix resin for prepregs, built-up laminate materials, resin for fiber reinforced plastics, sealing resin for liquid crystal display panels, paints, various coating agents, adhesives, and coatings for semiconductors installed in electronic equipment and industrial equipment It can be used widely and effectively in an agent, a resist resin for a semiconductor, a resin for forming a lower layer film and the like. In particular, the present invention can be used particularly effectively in the field of lithography lower layer films and multilayer resist lower layer films.

Claims

The compound represented by following formula (1).

(In the formula (1), each X independently represents an oxygen atom or a sulfur atom, or non-bridged, and R 1 is a single bond or a 2n-valent group having 1 to 30 carbon atoms, Each may have an alicyclic hydrocarbon group, a double bond, a hetero atom, or an aryl group having 6 to 30 carbon atoms, and each R 2 is independently a straight chain having 1 to 10 carbon atoms, A branched or cyclic alkyl group, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, or a hydroxyl group, And at least one of R 2 is an alkoxy group having 1 to 30 carbon atoms or an aryloxy group having 6 to 30 carbon atoms, m is each independently an integer of 1 to 6, and p is each independently 0 or 1 and n is an integer of 1 to 4.)
The compound according to claim 1, wherein the compound represented by the formula (1) is a compound represented by the following formula (1A-2).

(In the formula (1A-2), R 1 and p are the same as described above, R 6 has the same meaning as R 2 described in the formula (1), and each m 6 independently represents 1 to 3 Is an integer.)
The compound according to claim 1, wherein the compound represented by the formula (1) is a compound represented by the following formula (1B-2).

(In formula (1B-2), R 1 and p are as defined above, R 6 has the same meaning as R 2 described in formula (1), and m 6 is independently 1 to 3 Is an integer.)
The compound according to claim 2, wherein the compound represented by the formula (1A-2) is a compound represented by the following formula (BisN-1-CH1) or the following formula (BisN-1-CH2).
The compound according to claim 2, wherein the compound represented by the formula (1A-2) is a compound represented by the following formula (BisN-1-PH1) or the following formula (BisN-1-PH2).
A resin obtained by using the compound according to any one of claims 1 to 5 as a monomer.
The resin according to claim 6, which is obtained by a reaction between the compound according to any one of claims 1 to 5 and a compound having a crosslinking reactivity.
The crosslinking reactive compound is at least one selected from the group consisting of aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanates and unsaturated hydrocarbon group-containing compounds. The resin according to claim 7.
The resin according to claim 6, comprising a structure represented by the following formula (2).

(In the formula (2), each X independently represents an oxygen atom, a sulfur atom, or a non-bridged group, and R 1 is a single bond or a 2n-valent group having 1 to 30 carbon atoms. Each may have an alicyclic hydrocarbon group, a double bond, a hetero atom or an aryl group having 6 to 30 carbon atoms, and each R 2 is independently a straight chain having 1 to 10 carbon atoms. A branched or cyclic alkyl group, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, or a hydroxyl group, Here, at least one of R 2 is an alkoxy group having 1 to 30 carbon atoms or an aryloxy group having 6 to 30 carbon atoms, and each R 3 is independently a single bond or a straight chain having 1 to 20 carbon atoms. a Jo or branched alkylene group, m 2 are each independently 1 to Of integers, p is independently 0 or 1, n is an integer of 1-4.)
The resin according to claim 9, wherein the resin having a structure represented by the formula (2) is a resin having a structure represented by the following formula (2A).

(In formula (2A), R 1 , R 2 , R 3 , m 2 , p and n are the same as described above.)
The resin according to claim 9, wherein the resin having a structure represented by the formula (2) is a resin having a structure represented by the following formula (2B).

(In formula (2B), R 1 , R 2 , R 3 , m 2 , p and n are the same as described above.)
A material for forming an underlayer film for lithography, comprising the compound according to any one of claims 1 to 5 and / or the resin according to any one of claims 6 to 11.
The material for forming a lower layer film for lithography according to claim 12, further comprising an organic solvent.
The material for forming a lower layer film for lithography according to claim 12 or 13, further comprising an acid generator.
The material for forming an underlayer film for lithography according to any one of claims 12 to 14, further comprising a crosslinking agent.
A lithographic lower layer film formed from the lithographic lower layer film forming material according to any one of claims 12 to 15.
A step (A-1) of forming a lower layer film on the substrate using the lower layer film forming material for lithography according to any one of claims 12 to 15;
Forming at least one photoresist layer on the lower layer film (A-2);
After the step (A-2), a step of irradiating a predetermined region of the photoresist layer with radiation and developing (A-3);
A resist pattern forming method comprising:
A step (B-1) of forming a lower layer film on the substrate using the lower layer film forming material for lithography according to any one of claims 12 to 15;
Forming an intermediate layer film on the lower layer film using a resist intermediate layer film material containing silicon atoms (B-2);
Forming at least one photoresist layer on the intermediate film (B-3);
After the step (B-3), a step (B-4) of irradiating a predetermined region of the photoresist layer with radiation and developing to form a resist pattern;
After the step (B-4), the intermediate layer film is etched using the resist pattern as a mask, the lower layer film is etched using the obtained intermediate layer film pattern as an etching mask, and the obtained lower layer film pattern is etched. Forming a pattern on the substrate by etching the substrate as a mask (B-5);
A circuit pattern forming method.
An organic solvent which is not optionally miscible with water, and a solution (A) containing the compound according to any one of claims 1 to 5 or the resin according to any one of claims 6 to 11; A purification method comprising the step of extracting by contacting with an aqueous solution.